Patent Application
20220416170
The present invention relates to an organic electroluminescence device and an electronic device.
Organic electroluminescence devices (hereinafter also referred to as “organic EL devices”) are applied to full-color displays, for example, of mobile phones and televisions. When a voltage is applied to an organic EL device, holes are injected into an emitting layer from an anode, and electrons are injected into the emitting layer from a cathode. At the emitting layer, the injected holes and electrons recombine, producing excitons. Singlet excitons constitute 25% of the produced excitons, with triplet excitons constituting 75%, in accordance with the statistical law of electron spins.
To improve the performance of organic EL devices, researchers have conducted various studies on compounds used to make organic EL devices (see, for example, Patent Literatures 1 and 2). Patent Literatures 1 and 2 describe organic electroluminescence devices having a hole transporting layer in which a compound having an amine skeleton is contained.
Examples of performance attributes of an organic EL device include luminance, emission wavelength, chromaticity, luminous efficiency, drive voltage, and lifetime.
Patent Literature 1: WO 2009/145016
Patent Literature 2: WO 2010/061824
Patent Literature 3: WO 2016/133058
An object of the invention is to provide an organic electroluminescence device with reduced drive voltage and an electronic device incorporating this organic electroluminescence device.
According to an aspect of the invention, there is provided an organic electroluminescence device including an anode, a cathode, an emitting layer between the anode and the cathode, and a first hole transporting layer between the anode and the emitting layer, in which the first hole transporting layer is directly adjacent to the emitting layer, the first hole transporting layer contains a first compound represented by formula (1) below, and the first compound has at least one group represented by formula (11) below.
In formula (1),
R101 to R110 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; or a group represented by formula (11),
at least one of R101 to R110 is a group represented by formula (11);
when multiple groups represented by formula (11) are present, the multiple groups represented by formula (11) are mutually the same or different;
L101 is: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
Ar101 is: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
mx is 0, 1, 2, 3, 4, or 5;
when two or more L101s are present, the two or more L101s are mutually the same or different;
when two or more Ar101s are present, the two or more Ar101s are mutually the same or different;
* in formula (11) indicates a position of bonding with a pyrene ring in formula (1);
a substituent for “substituted or unsubstituted” group in the first compound is at least one group selected from the group consisting of: an unsubstituted alkyl group having 1 to 50 carbon atoms; an unsubstituted alkenyl group having 2 to 50 carbon atoms; an unsubstituted alkynyl group having 2 to 50 carbon atoms; an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; —Si(R901)(R902)(R903); —O—(R904); —S—(R905); a halogen atom; a cyano group; a nitro group; an unsubstituted aryl group having 6 to 50 ring carbon atoms; and an unsubstituted heterocyclic group having 5 to 50 ring atoms; in the first compound, represented by formula (1), R901, R902, R903, R904, R905, R801, and R802 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; when multiple R901s are present, the multiple R901s are mutually the same or different;
when multiple R902s are present, the multiple R902s are mutually the same or different;
when multiple R903s are present, the multiple R903s are mutually the same or different;
when multiple R904s are present, the multiple R904s are mutually the same or different;
when multiple R905s are present, the multiple R905s are mutually the same or different;
when multiple R801s are present, the multiple R801s are mutually the same or different; and
when multiple R802s are present, the multiple R802s are mutually the same or different.
According to another aspect of the invention, there is provided an electronic device incorporating the organic electroluminescence device according to the above aspect of the invention.
According to the above aspect of the invention, an organic electroluminescence device with reduced drive voltage can be provided. According to the above aspect of the invention, furthermore, an electronic device incorporating this organic electroluminescence device can be provided.
Herein, a hydrogen atom includes isotope having different numbers of neutrons, specifically, protium, deuterium and tritium.
In chemical formulae herein, it is assumed that a hydrogen atom (i.e. protium, deuterium and tritium) is bonded to each of bondable positions that are not annexed with signs “R” or the like or “D” representing a deuterium.
Herein, the ring carbon atoms refer to the number of carbon atoms among atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, cross-linking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring. When the ring is substituted by a substituent(s), carbon atom(s) contained in the substituent(s) is not counted in the ring carbon atoms. Unless otherwise specified, the same applies to the “ring carbon atoms” described later. For instance, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridine ring has 5 ring carbon atoms, and a furan ring has 4 ring carbon atoms. Further, for instance, 9,9-diphenylfluorenyl group has 13 ring carbon atoms and 9,9′-spirobifluorenyl group has 25 ring carbon atoms.
When a benzene ring is substituted by a substituent in a form of, for instance, an alkyl group, the number of carbon atoms of the alkyl group is not counted in the number of the ring carbon atoms of the benzene ring. Accordingly, the benzene ring substituted by an alkyl group has 6 ring carbon atoms. When a naphthalene ring is substituted by a substituent in a form of, for instance, an alkyl group, the number of carbon atoms of the alkyl group is not counted in the number of the ring carbon atoms of the naphthalene ring. Accordingly, the naphthalene ring substituted by an alkyl group has 10 ring carbon atoms.
Herein, the ring atoms refer to the number of atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, cross-linking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring (e.g., monocyclic ring, fused ring, and ring assembly). Atom(s) not forming the ring (e.g., hydrogen atom(s) for saturating the valence of the atom which forms the ring) and atom(s) in a substituent by which the ring is substituted are not counted as the ring atoms. Unless otherwise specified, the same applies to the “ring atoms” described later. For instance, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. For instance, the number of hydrogen atom(s) bonded to a pyridine ring or the number of atoms forming a substituent are not counted as the pyridine ring atoms. Accordingly, a pyridine ring bonded to a hydrogen atom(s) or a substituent(s) has 6 ring atoms. For instance, the hydrogen atom(s) bonded to carbon atom(s) of a quinazoline ring or the atoms forming a substituent are not counted as the quinazoline ring atoms. Accordingly, a quinazoline ring bonded to hydrogen atom(s) or a substituent(s) has 10 ring atoms.
Herein, “XX to YY carbon atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY carbon atoms” represent carbon atoms of an unsubstituted ZZ group and do not include carbon atoms of a substituent(s) of the substituted ZZ group. Herein, “YY” is larger than “XX,” “XX” representing an integer of 1 or more and “YY” representing an integer of 2 or more.
Herein, “XX to YY atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY atoms” represent atoms of an unsubstituted ZZ group and do not include atoms of a substituent(s) of the substituted ZZ group. Herein, “YY” is larger than “XX,” “XX” representing an integer of 1 or more and “YY” representing an integer of 2 or more.
Herein, an unsubstituted ZZ group refers to an “unsubstituted ZZ group” in a “substituted or unsubstituted ZZ group,” and a substituted ZZ group refers to a “substituted ZZ group” in a “substituted or unsubstituted ZZ group.”
Herein, the term “unsubstituted” used in a “substituted or unsubstituted ZZ group” means that a hydrogen atom(s) in the ZZ group is not substituted with a substituent(s). The hydrogen atom(s) in the “unsubstituted ZZ group” is protium, deuterium, or tritium.
Herein, the term “substituted” used in a “substituted or unsubstituted ZZ group” means that at least one hydrogen atom in the ZZ group is substituted with a substituent. Similarly, the term “substituted” used in a “BB group substituted by AA group” means that at least one hydrogen atom in the BB group is substituted with the AA group.
Substituents mentioned herein will be described below.
An “unsubstituted aryl group” mentioned herein has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
An “unsubstituted heterocyclic group” mentioned herein has, unless otherwise specified herein, 5 to 50, preferably 5 to 30, more preferably 5 to 18 ring atoms.
An “unsubstituted alkyl group” mentioned herein has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
An “unsubstituted alkenyl group” mentioned herein has, unless otherwise specified herein, 2 to 50, preferably 2 to 20, more preferably 2 to 6 carbon atoms.
An “unsubstituted alkynyl group” mentioned herein has, unless otherwise specified herein, 2 to 50, preferably 2 to 20, more preferably 2 to 6 carbon atoms.
An “unsubstituted cycloalkyl group” mentioned herein has, unless otherwise specified herein, 3 to 50, preferably 3 to 20, more preferably 3 to 6 ring carbon atoms.
An “unsubstituted arylene group” mentioned herein has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
An “unsubstituted divalent heterocyclic group” mentioned herein has, unless otherwise specified herein, 5 to 50, preferably 5 to 30, more preferably 5 to 18 ring atoms.
An “unsubstituted alkylene group” mentioned herein has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
Specific examples (specific example group G1) of the “substituted or unsubstituted aryl group” mentioned herein include unsubstituted aryl groups (specific example group G1A) below and substituted aryl groups (specific example group G1B) below. (Herein, an unsubstituted aryl group refers to an “unsubstituted aryl group” in a “substituted or unsubstituted aryl group”, and a substituted aryl group refers to a “substituted aryl group” in a “substituted or unsubstituted aryl group.”) A simply termed “aryl group” herein includes both of an “unsubstituted aryl group” and a “substituted aryl group.”
The “substituted aryl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted aryl group” with a substituent. Examples of the “substituted aryl group” include a group derived by substituting at least one hydrogen atom in the “unsubstituted aryl group” in the specific example group G1A below with a substituent, and examples of the substituted aryl group in the specific example group G1B below. It should be noted that the examples of the “unsubstituted aryl group” and the “substituted aryl group” mentioned herein are merely exemplary, and the “substituted aryl group” mentioned herein includes a group derived by further substituting a hydrogen atom bonded to a carbon atom of a skeleton of a “substituted aryl group” in the specific example group G1B below, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted aryl group” in the specific example group G1B below.
phenyl group, p-biphenyl group, m-biphenyl group, o-biphenyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-terphenyl-4-yl group, o-terphenyl-3-yl group, o-terphenyl-2-yl group, 1-naphthyl group, 2-naphthyl group, anthryl group, benzanthryl group, phenanthryl group, benzophenanthryl group, phenalenyl group, pyrenyl group, chrysenyl group, benzochrysenyl group, triphenylenyl group, benzotriphenylenyl group, tetracenyl group, pentacenyl group, fluorenyl group, 9,9′-spirobifluorenyl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, benzofluoranthenyl group, perylenyl group, and a monovalent aryl group derived by removing one hydrogen atom from cyclic structures represented by formulae (TEMP-1) to (TEMP-15) below.
o-tolyl group, m-tolyl group, p-tolyl group, para-xylyl group, meta-xylyl group, ortho-xylyl group, para-isopropylphenyl group, meta-isopropylphenyl group, ortho-isopropylphenyl group, para-t-butylphenyl group, meta-t-butylphenyl group, ortho-t-butylphenyl group, 3,4,5-trimethylphenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, 9,9-bis(4-methylphenyl)fluorenyl group, 9,9-bis(4-isopropylphenyl)fluorenyl group, 9,9-bis(4-t-butylphenyl)fluorenyl group, cyanophenyl group, triphenylsilylphenyl group, trimethylsilylphenyl group, phenylnaphthyl group, naphthylphenyl group, and a group derived by substituting at least one hydrogen atom of a monovalent group derived from one of the cyclic structures represented by formulae (TEMP-1) to (TEMP-15) with a substituent.
The “heterocyclic group” mentioned herein refers to a cyclic group having at least one hetero atom in the ring atoms. Specific examples of the hetero atom include a nitrogen atom, oxygen atom, sulfur atom, silicon atom, phosphorus atom, and boron atom.
The “heterocyclic group” mentioned herein is a monocyclic group or a fused-ring group.
The “heterocyclic group” mentioned herein is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
Specific examples (specific example group G2) of the “substituted or unsubstituted heterocyclic group” mentioned herein include unsubstituted heterocyclic groups (specific example group G2A) and substituted heterocyclic groups (specific example group G2B). (Herein, an unsubstituted heterocyclic group refers to an “unsubstituted heterocyclic group” in a “substituted or unsubstituted heterocyclic group,” and a substituted heterocyclic group refers to a “substituted heterocyclic group” in a “substituted or unsubstituted heterocyclic group.”) A simply termed “heterocyclic group” herein includes both of “unsubstituted heterocyclic group” and “substituted heterocyclic group.”
The “substituted heterocyclic group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted heterocyclic group” with a substituent. Specific examples of the “substituted heterocyclic group” include a group derived by substituting at least one hydrogen atom in the “unsubstituted heterocyclic group” in the specific example group G2A below with a substituent, and examples of the substituted heterocyclic group in the specific example group G2B below. It should be noted that the examples of the “unsubstituted heterocyclic group” and the “substituted heterocyclic group” mentioned herein are merely exemplary, and the “substituted heterocyclic group” mentioned herein includes a group derived by further substituting a hydrogen atom bonded to a ring atom of a skeleton of a “substituted heterocyclic group” in the specific example group G2B below, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted heterocyclic group” in the specific example group G2B below.
The specific example group G2A includes, for instance, unsubstituted heterocyclic groups including a nitrogen atom (specific example group G2A1) below, unsubstituted heterocyclic groups including an oxygen atom (specific example group G2A2) below, unsubstituted heterocyclic groups including a sulfur atom (specific example group G2A3) below, and monovalent heterocyclic groups (specific example group G2A4) derived by removing a hydrogen atom from cyclic structures represented by formulae (TEMP-16) to (TEMP-33) below.
The specific example group G2B includes, for instance, substituted heterocyclic groups including a nitrogen atom (specific example group G2B1) below, substituted heterocyclic groups including an oxygen atom (specific example group G2B2) below, substituted heterocyclic groups including a sulfur atom (specific example group G2B3) below, and groups derived by substituting at least one hydrogen atom of the monovalent heterocyclic groups (specific example group G2B4) derived from the cyclic structures represented by formulae (TEMP-16) to (TEMP-33) below.
pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, pyridyl group, pyridazynyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, indolyl group, isoindolyl group, indolizinyl group, quinolizinyl group, quinolyl group, isoquinolyl group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimidazolyl group, indazolyl group, phenanthrolinyl group, phenanthridinyl group, acridinyl group, phenazinyl group, carbazolyl group, benzocarbazolyl group, morpholino group, phenoxazinyl group, phenothiazinyl group, azacarbazolyl group, and diazacarbazolyl group.
furyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, xanthenyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, naphthobenzofuranyl group, benzoxazolyl group, benzisoxazolyl group, phenoxazinyl group, morpholino group, dinaphthofuranyl group, azadibenzofuranyl group, diazadibenzofuranyl group, azanaphthobenzofuranyl group, and diazanaphthobenzofuranyl group.
thienyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, benzothiophenyl group (benzothienyl group), isobenzothiophenyl group (isobenzothienyl group), dibenzothiophenyl group (dibenzothienyl group), naphthobenzothiophenyl group (nahthobenzothienyl group), benzothiazolyl group, benzisothiazolyl group, phenothiazinyl group, dinaphthothiophenyl group (dinaphthothienyl group), azadibenzothiophenyl group (azadibenzothienyl group), diazadibenzothiophenyl group (diazadibenzothienyl group), azanaphthobenzothiophenyl group (azanaphthobenzothienyl group), and diazanaphthobenzothiophenyl group (diazanaphthobenzothienyl group).
In formulae (TEMP-16) to (TEMP-33), XA and YA are each independently an oxygen atom, a sulfur atom, NH, or CH2, with a proviso that at least one of XA or YA is an oxygen atom, a sulfur atom, or NH.
When at least one of XA or YA in formulae (TEMP-16) to (TEMP-33) is NH or CH2, the monovalent heterocyclic groups derived from the cyclic structures represented by formulae (TEMP-16) to (TEMP-33) include a monovalent group derived by removing one hydrogen atom from NH or CH2.
(9-phenyl)carbazolyl group, (9-biphenylyl)carbazolyl group, (9-phenyl)phenylcarbazolyl group, (9-naphthyl)carbazolyl group, diphenylcarbazole-9-yl group, phenylcarbazole-9-yl group, methylbenzimidazolyl group, ethylbenzimidazolyl group, phenyltriazinyl group, biphenylyltriazinyl group, diphenyltriazinyl group, phenylquinazolinyl group, and biphenylquinazolinyl group.
phenyldibenzofuranyl group, methyldibenzofuranyl group, t-butyldibenzofuranyl group, and monovalent residue of spiro[9H-xanthene-9,9′-[9H]fluorene].
phenyldibenzothiophenyl group, methyldibenzothiophenyl group, t-butyldibenzothiophenyl group, and monovalent residue of spiro[9H-thioxanthene-9,9′-[9H]fluorene].
The “at least one hydrogen atom of a monovalent heterocyclic group” means at least one hydrogen atom selected from a hydrogen atom bonded to a ring carbon atom of the monovalent heterocyclic group, a hydrogen atom bonded to a nitrogen atom of at least one of XA or YA in a form of NH, and a hydrogen atom of one of XA and YA in a form of a methylene group (CH2).
Specific examples (specific example group G3) of the “substituted or unsubstituted alkyl group” mentioned herein include unsubstituted alkyl groups (specific example group G3A) and substituted alkyl groups (specific example group G3B) below. (Herein, an unsubstituted alkyl group refers to an “unsubstituted alkyl group” in a “substituted or unsubstituted alkyl group,” and a substituted alkyl group refers to a “substituted alkyl group” in a “substituted or unsubstituted alkyl group.”) A simply termed “alkyl group” herein includes both of “unsubstituted alkyl group” and “substituted alkyl group.”
The “substituted alkyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkyl group” with a substituent. Specific examples of the “substituted alkyl group” include a group derived by substituting at least one hydrogen atom of an “unsubstituted alkyl group” (specific example group G3A) below with a substituent, and examples of the substituted alkyl group (specific example group G3B) below. Herein, the alkyl group for the “unsubstituted alkyl group” refers to a chain alkyl group. Accordingly, the “unsubstituted alkyl group” include linear “unsubstituted alkyl group” and branched “unsubstituted alkyl group.” It should be noted that the examples of the “unsubstituted alkyl group” and the “substituted alkyl group” mentioned herein are merely exemplary, and the “substituted alkyl group” mentioned herein includes a group derived by further substituting a hydrogen atom of a skeleton of the “substituted alkyl group” in the specific example group G3B, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted alkyl group” in the specific example group G3B.
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.
heptafluoropropyl group (including isomer thereof), pentafluoroethyl group, 2,2,2-trifluoroethyl group, and trifluoromethyl group.
Specific examples (specific example group G4) of the “substituted or unsubstituted alkenyl group” mentioned herein include unsubstituted alkenyl groups (specific example group G4A) and substituted alkenyl groups (specific example group G4B). (Herein, an unsubstituted alkenyl group refers to an “unsubstituted alkenyl group” in a “substituted or unsubstituted alkenyl group,” and a substituted alkenyl group refers to a “substituted alkenyl group” in a “substituted or unsubstituted alkenyl group.”) A simply termed “alkenyl group” herein includes both of “unsubstituted alkenyl group” and “substituted alkenyl group.”
The “substituted alkenyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkenyl group” with a substituent. Specific examples of the “substituted alkenyl group” include an “unsubstituted alkenyl group” (specific example group G4A) substituted by a substituent, and examples of the substituted alkenyl group (specific example group G4B) below. It should be noted that the examples of the “unsubstituted alkenyl group” and the “substituted alkenyl group” mentioned herein are merely exemplary, and the “substituted alkenyl group” mentioned herein includes a group derived by further substituting a hydrogen atom of a skeleton of the “substituted alkenyl group” in the specific example group G4B with a substituent, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted alkenyl group” in the specific example group G4B with a substituent.
vinyl group, allyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group.
1,3-butanedienyl group, 1-methylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, and 1,2-dimethylallyl group.
Specific examples (specific example group G5) of the “substituted or unsubstituted alkynyl group” mentioned herein include unsubstituted alkynyl groups (specific example group G5A) below. (Herein, an unsubstituted alkynyl group refers to an “unsubstituted alkynyl group” in a “substituted or unsubstituted alkynyl group.”) A simply termed “alkynyl group” herein includes both of “unsubstituted alkynyl group” and “substituted alkynyl group.”
The “substituted alkynyl group” refers to a group derived by substituting at least one hydrogen atom in an “unsubstituted alkynyl group” with a substituent. Specific examples of the “substituted alkynyl group” include a group derived by substituting at least one hydrogen atom of the “unsubstituted alkynyl group” (specific example group G5A) below with a substituent.
ethynyl group.
Specific examples (specific example group G6) of the “substituted or unsubstituted cycloalkyl group” mentioned herein include unsubstituted cycloalkyl groups (specific example group G6A) and substituted cycloalkyl groups (specific example group G6B). (Herein, an unsubstituted cycloalkyl group refers to an “unsubstituted cycloalkyl group” in a “substituted or unsubstituted cycloalkyl group,” and a substituted cycloalkyl group refers to a “substituted cycloalkyl group” in a “substituted or unsubstituted cycloalkyl group.”) A simply termed “cycloalkyl group” herein includes both of “unsubstituted cycloalkyl group” and “substituted cycloalkyl group.”
The “substituted cycloalkyl group” refers to a group derived by substituting at least one hydrogen atom of an “unsubstituted cycloalkyl group” with a substituent. Specific examples of the “substituted cycloalkyl group” include a group derived by substituting at least one hydrogen atom of the “unsubstituted cycloalkyl group” (specific example group G6A) below with a substituent, and examples of the substituted cycloalkyl group (specific example group G6B) below. It should be noted that the examples of the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group” mentioned herein are merely exemplary, and the “substituted cycloalkyl group” mentioned herein includes a group derived by substituting at least one hydrogen atom bonded to a carbon atom of a skeleton of the “substituted cycloalkyl group” in the specific example group G6B with a substituent, and a group derived by further substituting a hydrogen atom of a substituent of the “substituted cycloalkyl group” in the specific example group G6B with a substituent.
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, and 2-norbornyl group.
4-methylcyclohexyl group.
Specific examples (specific example group G7) of the group represented herein by —Si(R901)(R902)(R903) include —Si(G1)(G1)(G1), —Si(G1)(G2)(G2), —Si(G1)(G1)(G2), —Si(G2)(G2)(G2), —Si(G3)(G3)(G3), and —Si(G6)(G6)(G6), where:
G1 represents a “substituted or unsubstituted aryl group” in the specific example group G1,
G2 represents a “substituted or unsubstituted heterocyclic group” in the specific example group G2,
G3 represents a “substituted or unsubstituted alkyl group” in the specific example group G3, and
G6 represents a “substituted or unsubstituted cycloalkyl group” in the specific example group G6,
a plurality of G1 in —Si(G1)(G1)(G1) are mutually the same or different,
a plurality of G2 in —Si(G1)(G2)(G2) are mutually the same or different,
a plurality of G1 in —Si(G1)(G1)(G2) are mutually the same or different,
a plurality of G2 in —Si(G2)(G2)(G2) are mutually the same or different,
a plurality of G3 in —Si(G3)(G3)(G3) are mutually the same or different, and
a plurality of G6 in —Si(G6)(G6)(G6) are mutually the same or different.
Specific examples (specific example group G8) of a group represented by —O—(R904) herein include —O(G1), —O(G2), —O(G3), and —O(G6), where:
G1 represents a “substituted or unsubstituted aryl group” in the specific example group G1,
G2 represents a “substituted or unsubstituted heterocyclic group” in the specific example group G2,
G3 represents a “substituted or unsubstituted alkyl group” in the specific example group G3, and
G6 represents a “substituted or unsubstituted cycloalkyl group” in the specific example group G6.
Specific examples (specific example group G9) of a group represented herein by —S—(R905) include —S(G1), —S(G2), —S(G3), and —S(G6), where:
G1 represents a “substituted or unsubstituted aryl group” in the specific example group G1,
G2 represents a “substituted or unsubstituted heterocyclic group” in the specific example group G2,
G3 represents a “substituted or unsubstituted alkyl group” in the specific example group G3, and
G6 represents a “substituted or unsubstituted cycloalkyl group” in the specific example group G6.
Group Represented by —N(R906)(R907)
Specific examples (specific example group G10) of a group represented herein by —N(R906)(R907) include —N(G1)(G1), —N(G2)(G2), —N(G1)(G2), —N(G3)(G3), and —N(G6)(G6), where:
G1 represents a “substituted or unsubstituted aryl group” in the specific example group G1,
G2 represents a “substituted or unsubstituted heterocyclic group” in the specific example group G2,
G3 represents a “substituted or unsubstituted alkyl group” in the specific example group G3,
G6 represents a “substituted or unsubstituted cycloalkyl group” in the specific example group G6,
a plurality of G1 in —N(G1)(G1) are mutually the same or different,
a plurality of G2 in —N(G2)(G2) are mutually the same or different,
a plurality of G3 in —N(G3)(G3) are mutually the same or different, and
a plurality of G6 in —N(G6)(G6) are mutually the same or different.
Specific examples (specific example group G11) of “halogen atom” mentioned herein include a fluorine atom, chlorine atom, bromine atom, and iodine atom.
The “substituted or unsubstituted fluoroalkyl group” mentioned herein refers to a group derived by substituting at least one hydrogen atom bonded to at least one of carbon atoms forming an alkyl group in the “substituted or unsubstituted alkyl group” with a fluorine atom, and also includes a group (perfluoro group) derived by substituting all of hydrogen atoms bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with fluorine atoms. An “unsubstituted fluoroalkyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms. The “substituted fluoroalkyl group” refers to a group derived by substituting at least one hydrogen atom in a “fluoroalkyl group” with a substituent. It should be noted that the examples of the “substituted fluoroalkyl group” mentioned herein include a group derived by further substituting at least one hydrogen atom bonded to a carbon atom of an alkyl chain of a “substituted fluoroalkyl group” with a substituent, and a group derived by further substituting at least one hydrogen atom of a substituent of the “substituted fluoroalkyl group” with a substituent. Specific examples of the “substituted fluoroalkyl group” include a group derived by substituting at least one hydrogen atom of the “alkyl group” (specific example group G3) with a fluorine atom.
The “substituted or unsubstituted haloalkyl group” mentioned herein refers to a group derived by substituting at least one hydrogen atom bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with a halogen atom, and also includes a group derived by substituting all hydrogen atoms bonded to carbon atoms forming the alkyl group in the “substituted or unsubstituted alkyl group” with halogen atoms. An “unsubstituted haloalkyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms. The “substituted haloalkyl group” refers to a group derived by substituting at least one hydrogen atom in a “haloalkyl group” with a substituent. It should be noted that the examples of the “substituted haloalkyl group” mentioned herein include a group derived by further substituting at least one hydrogen atom bonded to a carbon atom of an alkyl chain of a “substituted haloalkyl group” with a substituent, and a group derived by further substituting at least one hydrogen atom of a substituent of the “substituted haloalkyl group” with a substituent. Specific examples of the “unsubstituted haloalkyl group” include a group derived by substituting at least one hydrogen atom of the “alkyl group” (specific example group G3) with a halogen atom. The haloalkyl group is sometimes referred to as a halogenated alkyl group.
Specific examples of a “substituted or unsubstituted alkoxy group” mentioned herein include a group represented by —O(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. An “unsubstituted alkoxy group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms.
Specific examples of a “substituted or unsubstituted alkylthio group” mentioned herein include a group represented by —S(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. An “unsubstituted alkylthio group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 30, more preferably 1 to 18 carbon atoms.
Specific examples of a “substituted or unsubstituted aryloxy group” mentioned herein include a group represented by —O(G1), G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. An “unsubstituted aryloxy group” has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
Specific examples of a “substituted or unsubstituted arylthio group” mentioned herein include a group represented by —S(G1), G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. An “unsubstituted arylthio group” has, unless otherwise specified herein, 6 to 50, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms.
Specific examples of a “trialkylsilyl group” mentioned herein include a group represented by —Si(G3)(G3)(G3), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3. The plurality of G3 in —Si(G3)(G3)(G3) are mutually the same or different. Each of the alkyl groups in the “trialkylsilyl group” has, unless otherwise specified herein, 1 to 50, preferably 1 to 20, more preferably 1 to 6 carbon atoms.
Specific examples of a “substituted or unsubstituted aralkyl group” mentioned herein include a group represented by (G3)-(G1), G3 being the “substituted or unsubstituted alkyl group” in the specific example group G3, G1 being the “substituted or unsubstituted aryl group” in the specific example group G1. Accordingly, the “aralkyl group” is a group derived by substituting a hydrogen atom of the “alkyl group” with a substituent in a form of the “aryl group,” which is an example of the “substituted alkyl group.” An “unsubstituted aralkyl group,” which is an “unsubstituted alkyl group” substituted by an “unsubstituted aryl group,” has, unless otherwise specified herein, 7 to 50 carbon atoms, preferably 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms.
Specific examples of the “substituted or unsubstituted aralkyl group” include a benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, and 2-β-naphthylisopropyl group.
Preferable examples of the substituted or unsubstituted aryl group mentioned herein include, unless otherwise specified herein, a phenyl group, p-biphenyl group, m-biphenyl group, o-biphenyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-terphenyl-4-yl group, o-terphenyl-3-yl group, o-terphenyl-2-yl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, fluorenyl group, 9,9′-spirobifluorenyl group, 9,9-dimethylfluorenyl group, and 9,9-diphenylfluorenyl group.
Preferable examples of the substituted or unsubstituted heterocyclic group mentioned herein include, unless otherwise specified herein, a pyridyl group, pyrimidinyl group, triazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, benzimidazolyl group, phenanthrolinyl group, carbazolyl group (1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, or 9-carbazolyl group), benzocarbazolyl group, azacarbazolyl group, diazacarbazolyl group, dibenzofuranyl group, naphthobenzofuranyl group, azadibenzofuranyl group, diazadibenzofuranyl group, dibenzothiophenyl group, naphthobenzothiophenyl group, azadibenzothiophenyl group, diazadibenzothiophenyl group, (9-phenyl)carbazolyl group ((9-phenyl)carbazole-1-yl group, (9-phenyl)carbazole-2-yl group, (9-phenyl)carbazole-3-yl group, or (9-phenyl)carbazole-4-yl group), (9-biphenylyl)carbazolyl group, (9-phenyl)phenylcarbazolyl group, diphenylcarbazole-9-yl group, phenylcarbazole-9-yl group, phenyltriazinyl group, biphenylyltriazinyl group, diphenyltriazinyl group, phenyldibenzofuranyl group, and phenyldibenzothiophenyl group.
The carbazolyl group mentioned herein is, unless otherwise specified herein, specifically a group represented by one of formulae below.
The (9-phenyl)carbazolyl group mentioned herein is, unless otherwise specified herein, specifically a group represented by one of formulae below.
In formulae (TEMP-Cz1) to (TEMP-Cz9), * represents a bonding position.
The dibenzofuranyl group and dibenzothiophenyl group mentioned herein are, unless otherwise specified herein, each specifically represented by one of formulae below.
In formulae (TEMP-34) to (TEMP-41), * represents a bonding position.
Preferable examples of the substituted or unsubstituted alkyl group mentioned herein include, unless otherwise specified herein, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
The “substituted or unsubstituted arylene group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on an aryl ring of the “substituted or unsubstituted aryl group.” Specific examples of the “substituted or unsubstituted arylene group” (specific example group G12) include a divalent group derived by removing one hydrogen atom on an aryl ring of the “substituted or unsubstituted aryl group” in the specific example group G1.
The “substituted or unsubstituted divalent heterocyclic group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on a heterocycle of the “substituted or unsubstituted heterocyclic group.” Specific examples of the “substituted or unsubstituted divalent heterocyclic group” (specific example group G13) include a divalent group derived by removing one hydrogen atom on a heterocyclic ring of the “substituted or unsubstituted heterocyclic group” in the specific example group G2.
The “substituted or unsubstituted alkylene group” mentioned herein is, unless otherwise specified herein, a divalent group derived by removing one hydrogen atom on an alkyl chain of the “substituted or unsubstituted alkyl group.” Specific examples of the “substituted or unsubstituted alkylene group” (specific example group G14) include a divalent group derived by removing one hydrogen atom on an alkyl chain of the “substituted or unsubstituted alkyl group” in the specific example group G3.
The substituted or unsubstituted arylene group mentioned herein is, unless otherwise specified herein, preferably any one of groups represented by formulae (TEMP-42) to (TEMP-68) below.
In formulae (TEMP-42) to (TEMP-52), Q1 to Q10 are each independently a hydrogen atom or a substituent.
In formulae (TEMP-42) to (TEMP-52), * represents a bonding position.
In formulae (TEMP-53) to (TEMP-62), Q1 to Q10 are each independently a hydrogen atom or a substituent.
In formulae, Q9 and Q10 may be mutually bonded through a single bond to form a ring.
In formulae (TEMP-53) to (TEMP-62), * represents a bonding position.
In formulae (TEMP-63) to (TEMP-68), Q1 to Q8 are each independently a hydrogen atom or a substituent.
In formulae (TEMP-63) to (TEMP-68), * represents a bonding position.
The substituted or unsubstituted divalent heterocyclic group mentioned herein is, unless otherwise specified herein, preferably a group represented by any one of formulae (TEMP-69) to (TEMP-102) below.
In formulae (TEMP-69) to (TEMP-82), Q1 to Q9 are each independently a hydrogen atom or a substituent.
In formulae (TEMP-83) to (TEMP-102), Q1 to Q8 are each independently a hydrogen atom or a substituent.
The substituent mentioned herein has been described above.
Instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring, mutually bonded to form a substituted or unsubstituted fused ring, or not mutually bonded” mentioned herein refer to instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring, “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring,” and “at least one combination of adjacent two or more (of . . . ) are not mutually bonded.”
Instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring” and “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring” mentioned herein (these instances will be sometimes collectively referred to as an instance of “bonded to form a ring” hereinafter) will be described below. An anthracene compound having a basic skeleton in a form of an anthracene ring and represented by formula (TEMP-103) below will be used as an example for the description.
For instance, when “at least one combination of adjacent two or more of R921 to R930 are mutually bonded to form a ring,” the combination of adjacent ones of R921 to R930 (i.e. the combination at issue) is a combination of R921 and R922, a combination of R922 and R923, a combination of R923 and R924, a combination of R924 and R930, a combination of R930 and R925, a combination of R925 and R926, a combination of R926 and R927, a combination of R927 and R928, a combination of R928 and R929, or a combination of R929 and R921.
The term “at least one combination” means that two or more of the above combinations of adjacent two or more of R921 to R930 may simultaneously form rings. For instance, when R921 and R922 are mutually bonded to form a ring QA and R925 and R926 are simultaneously mutually bonded to form a ring QB, the anthracene compound represented by formula (TEMP-103) is represented by formula (TEMP-104) below.
The instance where the “combination of adjacent two or more” form a ring means not only an instance where the “two” adjacent components are bonded but also an instance where adjacent “three or more” are bonded. For instance, R921 and R922 are mutually bonded to form a ring QA and R922 and R923 are mutually bonded to form a ring QC, and mutually adjacent three components (R921, R922 and R923) are mutually bonded to form a ring fused to the anthracene basic skeleton. In this case, the anthracene compound represented by formula (TEMP-103) is represented by formula (TEMP-105) below. In formula (TEMP-105) below, the ring QA and the ring QC share R922.
The formed “monocyclic ring” or “fused ring” may be, in terms of the formed ring in itself, a saturated ring or an unsaturated ring. When the “combination of adjacent two” form a “monocyclic ring” or a “fused ring,” the “monocyclic ring” or “fused ring” may be a saturated ring or an unsaturated ring. For instance, the ring QA and the ring QB formed in formula (TEMP-104) are each independently a “monocyclic ring” or a “fused ring.” Further, the ring QA and the ring QC formed in formula (TEMP-105) are each a “fused ring.” The ring QA and the ring QC in formula (TEMP-105) are fused to form a fused ring. When the ring QA in formula (TEMP-104) is a benzene ring, the ring QA is a monocyclic ring. When the ring QA in formula (TEMP-104) is a naphthalene ring, the ring QA is a fused ring.
The “unsaturated ring” represents an aromatic hydrocarbon ring or an aromatic heterocycle. The “saturated ring” represents an aliphatic hydrocarbon ring or a non-aromatic heterocycle.
Specific examples of the aromatic hydrocarbon ring include a ring formed by terminating a bond of a group in the specific example of the specific example group G1 with a hydrogen atom.
Specific examples of the aromatic heterocycle include a ring formed by terminating a bond of an aromatic heterocyclic group in the specific example of the specific example group G2 with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include a ring formed by terminating a bond of a group in the specific example of the specific example group G6 with a hydrogen atom.
The phrase “to form a ring” herein means that a ring is formed only by a plurality of atoms of a basic skeleton, or by a combination of a plurality of atoms of the basic skeleton and one or more optional atoms. For instance, the ring QA formed by mutually bonding R921 and R922 shown in formula (TEMP-104) is a ring formed by a carbon atom of the anthracene skeleton bonded to R921, a carbon atom of the anthracene skeleton bonded to R922, and one or more optional atoms. Specifically, when the ring QA is a monocyclic unsaturated ring formed by R921 and R922, the ring formed by a carbon atom of the anthracene skeleton bonded to R921, a carbon atom of the anthracene skeleton bonded to R922, and four carbon atoms is a benzene ring.
The “optional atom” is, unless otherwise specified herein, preferably at least one atom selected from the group consisting of a carbon atom, nitrogen atom, oxygen atom, and sulfur atom. A bond of the optional atom (e.g. a carbon atom and a nitrogen atom) not forming a ring may be terminated by a hydrogen atom or the like or may be substituted by an “optional substituent” described later. When the ring includes an optional element other than carbon atom, the resultant ring is a heterocycle.
The number of “one or more optional atoms” forming the monocyclic ring or fused ring is, unless otherwise specified herein, preferably in a range from 2 to 15, more preferably in a range from 3 to 12, further preferably in a range from 3 to 5.
Unless otherwise specified herein, the ring, which may be a “monocyclic ring” or “fused ring,” is preferably a “monocyclic ring.”
Unless otherwise specified herein, the ring, which may be a “saturated ring” or “unsaturated ring,” is preferably an “unsaturated ring.”
Unless otherwise specified herein, the “monocyclic ring” is preferably a benzene ring.
Unless otherwise specified herein, the “unsaturated ring” is preferably a benzene ring.
When “at least one combination of adjacent two or more” (of . . . ) are “mutually bonded to form a substituted or unsubstituted monocyclic ring” or “mutually bonded to form a substituted or unsubstituted fused ring,” unless otherwise specified herein, at least one combination of adjacent two or more of components are preferably mutually bonded to form a substituted or unsubstituted “unsaturated ring” formed of a plurality of atoms of the basic skeleton, and 1 to 15 atoms of at least one element selected from the group consisting of carbon, nitrogen, oxygen and sulfur.
When the “monocyclic ring” or the “fused ring” has a substituent, the substituent is the substituent described in later-described “optional substituent.” When the “monocyclic ring” or the “fused ring” has a substituent, specific examples of the substituent are the substituents described in the above under the subtitle “Substituent Mentioned Herein.”.
When the “saturated ring” or the “unsaturated ring” has a substituent, the substituent is the substituent described in later-described “optional substituent.” When the “monocyclic ring” or the “fused ring” has a substituent, specific examples of the substituent are the substituents described in the above under the subtitle “Substituent Mentioned Herein.”
The above is the description for the instances where “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted monocyclic ring” and “at least one combination of adjacent two or more (of . . . ) are mutually bonded to form a substituted or unsubstituted fused ring” mentioned herein (sometimes referred to as an instance of “bonded to form a ring”).
In an exemplary embodiment herein, a substituent for the substituted or unsubstituted group (sometimes referred to as an “optional substituent” hereinafter) is, for instance, a group selected from the group consisting of an unsubstituted alkyl group having 1 to 50 carbon atoms, an unsubstituted alkenyl group having 2 to 50 carbon atoms, an unsubstituted alkynyl group having 2 to 50 carbon atoms, an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, —Si(R901)(R902)(R903), —O—(R904), —S—(R905), —N(R906)(R907), a halogen atom, a cyano group, a nitro group, an unsubstituted aryl group having 6 to 50 ring carbon atoms, and an unsubstituted heterocyclic group having 5 to 50 ring atoms.
R901 to R907 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
When two or more R901 are present, the two or more R901 are mutually the same or different,
when two or more R902 are present, the two or more R902 are mutually the same or different,
when two or more R903 are present, the two or more R903 are mutually the same or different,
when two or more R904 are present, the two or more R904 are mutually the same or different,
when two or more R905 are present, the two or more R905 are mutually the same or different,
when two or more R906 are present, the two or more R906 are mutually the same or different, and
when two or more R907 are present, the two or more R907 are mutually the same or different.
In an exemplary embodiment, a substituent for the substituted or unsubstituted group is selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 ring carbon atoms, and a heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, a substituent for the substituted or unsubstituted group is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 ring carbon atoms, and a heterocyclic group having 5 to 18 ring atoms.
Specific examples of the above optional substituent are the same as the specific examples of the substituent described in the above under the subtitle “Substituent Mentioned Herein.”
Unless otherwise specified herein, adjacent ones of the optional substituents may form a “saturated ring” or an “unsaturated ring,” preferably a substituted or unsubstituted saturated five-membered ring, a substituted or unsubstituted saturated six-membered ring, a substituted or unsubstituted unsaturated five-membered ring, or a substituted or unsubstituted unsaturated six-membered ring, more preferably a benzene ring.
Unless otherwise specified herein, the optional substituent may further include a substituent. Examples of the substituent for the optional substituent are the same as the examples of the optional substituent.
Herein, numerical ranges represented by “AA to BB” represent a range whose lower limit is the value (AA) recited before “to” and whose upper limit is the value (BB) recited after “to.”
An organic electroluminescence device according to a first exemplary embodiment includes an anode, a cathode, an emitting layer between the anode and the cathode, and a first hole transporting layer between the anode and the emitting layer, in which the first hole transporting layer is directly adjacent to the emitting layer, the first hole transporting layer contains a first compound represented by formula (1) below, and the first compound has at least one group represented by formula (11) below.
Preferably, the organic electroluminescence device according to this exemplary embodiment emits light with a maximum peak wavelength in a range from 430 nm to 480 nm when driven.
The measurement of the maximum peak wavelength of the light emitted by the driven organic EL device is done as follows. A voltage is applied to the organic EL device to a current density of 10 mA/cm2, and the spectral radiance spectrum in this state is measured with CS-2000 spectroradiometer (Konica Minolta Holdings). In the spectral radiance spectrum obtained, the peak wavelength of the emission spectrum at which the luminous intensity peaks is measured, and defined as the maximum peak wavelength (unit: nm).
The organic EL device according to this exemplary embodiment may have one or more organic layers besides the emitting layer and the first hole transporting layer. The organic layer(s) can be, for example, at least any layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an emitting layer, an electron injecting layer, an electron transporting layer, a hole blocking layer, and an electron blocking layer.
The organic EL device according to this exemplary embodiment may consist of the emitting layer and the first hole transporting layer as organic layers, but alternatively, the device may further have, for example, at least any layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, etc.
Preferably, the organic EL device according to this exemplary embodiment has an electron transporting layer between the cathode and the emitting layer.
The organic EL device 1 includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10 between the anode 3 and the cathode 4. The organic layer 10 is formed by a hole injecting layer 6, a first hole transporting layer 71, an emitting layer 5, an electron transporting layer 8, and an electron injecting layer 9 stacked in this order on the anode 3.
The first hole transporting layer is directly adjacent to the emitting layer. The first hole transporting layer contains a first compound represented by formula (1) below.
Preferably, the thickness of the first hole transporting layer is 15 nm or less.
Preferably, the thickness of the first hole transporting layer is 2 nm or more.
More preferably, the thickness of the first hole transporting layer is in a range from 2 nm to 10 nm, even more preferably in a range from 2 nm to 5 nm.
The first compound is a compound represented by formula (1) below. The first compound has at least one group represented by formula (11) below.
In formula (1),
R101 to R110 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; or a group represented by formula (11);
at least one of R101 to R110 is a group represented by formula (11);
when multiple groups represented by formula (11) are present, the multiple groups represented by formula (11) are mutually the same or different;
L101 is: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
Ar101 is: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
mx is 0, 1, 2, 3, 4, or 5;
when two or more L101s are present, the two or more L101s are mutually the same or different;
when two or more Ar101s are present, the two or more Ar101s are mutually the same or different; and
* in formula (11) indicates the position of bonding with the pyrene ring in formula (1).
A substituent for “substituted or unsubstituted” group in the first compound is at least any one selected from the group consisting of: an unsubstituted alkyl group having 1 to 50 carbon atoms; an unsubstituted alkenyl group having 2 to 50 carbon atoms; an unsubstituted alkynyl group having 2 to 50 carbon atoms; an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; —Si(R901)(R902)(R903); —O—(R904); —S—(R905); a halogen atom; a cyano group; a nitro group; an unsubstituted aryl group having 6 to 50 ring carbon atoms; and an unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the first compound, represented by formula (1), R901, R902, R903, R904, R905, R905, R907, R801, and R802 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; when multiple R901s are present, the multiple R901s are mutually the same or different;
when multiple R902s are present, the multiple R902s are mutually the same or different;
when multiple R903s are present, the multiple R903s are mutually the same or different;
when multiple R904s are present, the multiple R904s are mutually the same or different;
when multiple R905s are present, the multiple R905s are mutually the same or different;
when multiple R906s are present, the multiple R906s are mutually the same or different;
when multiple R907s are present, the multiple R907s are mutually the same or different;
when multiple R801s are present, the multiple R801s are mutually the same or different; and when multiple R802s are present, the multiple R802s are mutually the same or different.
Preferably, any heterocyclic group in the first compound is a group containing at least any of an oxygen or sulfur atom.
Preferably, the group represented by formula (11) is a group represented by formula (111) below.
In formula (111),
X1 is CR123R124, an oxygen atom, a sulfur atom, or NR125;
L111 and L112 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
ma is 0, 1, 2, 3, or 4;
mb is 0, 1, 2, 3, or 4;
ma+mb is 0, 1, 2, 3, or 4;
Ar101 represents the same as Ar101 in formula (11);
R121, R122, R123, R124, and R125 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
mc is 3;
the three R121s are mutually the same or different;
md is 3; and
the three R122s are mutually the same or different.
Among positions *1 to *8 of carbon atoms in a cyclic structure represented by formula (111a) below in a group represented by formula (111), L111 is bonded to one of the positions *1 to *4, R121 is bonded to each of three positions of the rest of *1 to *4, L112 is bonded to one of the positions *5 to *8, and R122 is bonded to each of three positions of the rest of *5 to *8.
For instance, in a group represented by formula (111), when L111 is bonded to a carbon atom at a position *2 in the cyclic structure represented by formula (111a) and L112 is bonded to a carbon atom at a position *7 in the cyclic structure represented by formula (111a), the group represented by formula (111) is represented by formula (111b) below.
In formula (111b),
X1, L111, L112, ma, mb, Ar101, R121, R122, R123, R124, and R125 each independently represent the same as X1, L111, L112, ma, mb, Ar101, R121, R122, R123, R124, and R125 in formula (111);
the multiple R121s are mutually the same or different; and
the multiple R122s are mutually the same or different.
In the organic EL device according to this exemplary embodiment, it is preferred that the group represented by formula (111) be a group represented by formula (111b).
In the organic EL device according to this exemplary embodiment, it is preferred that ma be 0, 1, or 2 and mb be 0, 1, or 2.
In the organic EL device according to this exemplary embodiment, it is preferred that ma be 0 or 1 and mb be 0 or 1.
If, in a group represented by formula (111), ma is 0 and if mb is 1, the group represented by formula (111) is represented by formula (111c) below.
In formula (111c), X1, L112, mc, md, Ar101, R121, and R122 each independently represent the same as X1, L112, mc, md, Ar101, R121, and R122 in formula (111).
In the organic EL device according to this exemplary embodiment, it is preferred that Ar101 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that Ar101 be a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted fluorenyl group.
In the organic EL device according to this exemplary embodiment, it is also preferred that Ar101 be a group represented by formula (12), (13), or (14) below.
In formulae (12), (13), and (14),
R111 to R120 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); group represented by —N(R906)(R907); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R124; a group represented by —COOR125; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; and
* in formulae (12), (13), and (14) indicates the position of bonding with L101 in formula (11) or that with L112 in formula (111), (111 b), or (111c).
It is also preferred that R124 and R125 in formulae (12), (13), and (14) each independently represent the same as R801 and R802 in the foregoing.
Preferably, the first compound is represented by formula (101) below.
In formula (101),
R101 to R120 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
one of R101 to R110 indicates a position of bonding with L101, and one of R111 to R120 indicates a position of bonding with L101;
L101 is: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
mx is 0, 1, 2, 3, 4, or 5; and
when two or more L101s are present, the two or more L101s are mutually the same or different.
If, in formula (101), R103 is a position of bonding with L101 and if R120 is a position of bonding with L101, the compounds represented by formula (101) are represented by formula (101A) below.
In formula (101A), R101, R102, R104 to R119, L101, and mx represent the same as R101, R102, R104 to R119, L101, and mx, respectively, in formula (101).
In the organic EL device according to this exemplary embodiment, it is preferred that L101 be a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that the first compound be represented by formula (102) below.
In formula (102),
R101 to R120 each independently represent the same as R101 to R120 in formula (101);
one of R101 to R110 indicates a position of bonding with L111, and one of R111 to R120 indicates a position of bonding with L112;
X1 is CR123R124, an oxygen atom, a sulfur atom, or NR125;
L111 and L112 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
ma is 0, 1, 2, 3, or 4;
mb is 0, 1, 2, 3, or 4;
ma+mb is 0, 1, 2, 3, or 4;
R121, R122, R123, R124, and R125 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
mc is 3;
the three R121s are mutually the same or different;
md is 3; and
the three R122s are mutually the same or different.
In the compounds represented by formula (102), it is preferred that ma be 0, 1, or 2 and mb be 0,1, or 2.
In the compounds represented by formula (102), it is preferred that ma be 0 or 1 and mb be 0 or 1.
In the organic EL device according to this exemplary embodiment, it is preferred that two or more of R101 to R110 be groups represented by formula (11).
In the organic EL device according to this exemplary embodiment, it is preferred that two or more of R101 to R110 be groups represented by formula (11) and Ar101 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that Ar101 be not a substituted or unsubstituted pyrenyl group; L101 be not a substituted or unsubstituted pyrenylene group; and any substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms as any of R101 to R110 not being the group represented by formula (11) be not a substituted or unsubstituted pyrenyl group.
In the organic EL device according to this exemplary embodiment, it is preferred that R101 to R110 not being the group represented by formula (11) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that: R101 to R110 not being the group represented by formula (11) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that R101 to R110 not being the group represented by formula (11) be hydrogen atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that X1 be CR123R124. For example, if X1 is CR123R124, the group represented by formula (111) is represented by formula (111d) below.
In formula (111d), L111, L112, ma, mb, ma+mb, Ar101, R121, R122, R123, R124, R125, mc, and md are each as defined in formula (111).
In the organic EL device according to this exemplary embodiment, it is preferred that R123 and R124 be not bonded together.
In the organic EL device according to this exemplary embodiment, it is preferred that at least one of L111 or L112 is: a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms.
In the first compound, examples of the substituent for “substituted or unsubstituted” group does not include a substituted or unsubstituted pyrenyl group.
In an exemplary embodiment, the first compound is a compound having only one pyrene ring in its molecule (also referred to as a monopyrene compound).
In an exemplary embodiment, the first compound is a compound having only two pyrene rings in its molecule (also referred to as a bispyrene compound).
In the first compound, it is preferred that all groups described as “substituted or unsubstituted” be “unsubstituted” groups.
Preferably, the first hole transporting layer contains no compound having an amino group.
Preferably, the first hole transporting layer contains no compound containing nitrogen and boron atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that the content ratio of the first compound in the first hole transporting layer be 90% by mass or more, more preferably 99% by mass or more.
In the organic EL device according to this exemplary embodiment, it is even more preferred that the first hole transporting layer consists of the first compound.
In the organic EL device according to this exemplary embodiment, it is preferred that the first hole transporting layer does not emit light with a maximum peak wavelength in a range from 430 nm to 480 nm when the device is driven.
The first compound can be produced by methods known in the related art. Alternatively, the first compound can be produced based on a method known in the related art by selecting known alternative reaction(s) and materials according to the final product.
Specific examples of first compounds include, for instance, the following compounds, although the invention is not limited to these specific examples of first compounds.
In the organic EL device according to this exemplary embodiment, it is preferred that the emitting layer contain second compound(s) that fluoresces.
If the emitting layer of the organic EL device according to this exemplary embodiment contains second compound(s) and a third compound, it is preferred that the third compound be a host material (also referred to as a matrix material), and it is preferred that the second compound(s) be dopant material(s) (also referred to as guest material(s), emitter(s), or luminescent material(s)).
As mentioned herein, a “host material” is, for example, a material that constitutes “50% by mass or more of the layer.” This means the emitting layer contains, for example, a third compound represented by formula (1) above or by formula (2) below at 50% by mass or more of its total mass. Alternatively, a “host material” may constitute, for example, 60% by mass or more of the layer, 70% by mass or more of the layer, 80% by mass or more of the layer, 90% by mass or more of the layer, or 95% by mass or more of the layer.
In the organic EL device according to this exemplary embodiment, it is also preferred that the emitting layer contain a pyrene derivative, more preferably a pyrene derivative as a host material.
In the organic EL device according to this exemplary embodiment, it is also preferred that the emitting layer contain an anthracene derivative, more preferably an anthracene derivative as a host material.
Preferably, the emitting layer contains no phosphorescent material as a dopant material.
Preferably, furthermore, the emitting layer contains no heavy metal complex and no phosphorescent rare earth metal complex. In this context, examples of heavy metal complexes include, for instance, iridium complexes, osmium complexes, and platinum complexes.
It is also preferred that the emitting layer contain no metal complex.
An emitting layer of an organic EL device according to an exemplary embodiment may be composed of multiple emitting layers.
An emitting layer of an organic EL device according to an exemplary embodiment includes, for example, a first emitting layer and a second emitting layer between the first emitting layer and the cathode. In this case, the organic EL device includes a first hole transporting layer, a first emitting layer, and a second emitting layer in this order from the anode, and the first hole transporting layer and the first emitting layer are in direct contact. Preferably, the first emitting layer is in direct contact with the second emitting layer.
The organic EL device 1B includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10 between the anode 3 and the cathode 4. The organic layer 10 is formed by a hole injecting layer 6, a first hole transporting layer 71, an emitting layer 5, an electron transporting layer 8, and an electron injecting layer 9 stacked in this order on the anode 3, and the emitting layer 5 includes a first emitting layer 51 and a second emitting layer 52.
Preferably, the first and second emitting layers each independently further contain a fluorescent compound.
Preferably, the fluorescent compounds contained in the first and second emitting layers are compounds that exhibit light emission with a maximum peak wavelength in a range from 430 nm to 480 nm.
It is also preferred that the first emitting layer contain second compound(s) that fluoresces and a third compound. In that case, it is preferred that the third compound, in the first emitting layer, be a host material (also referred to as a matrix material), and it is preferred that the second compound(s) be dopant material(s) (also referred to as guest material(s), emitter(s), or luminescent material(s)).
It is also preferred that the second emitting layer contain fourth compound(s) that fluoresces and a fifth compound. In that case, it is preferred that the fifth compound, in the second emitting layer, be a host material (also referred to as a matrix material), and it is preferred that the fourth compound(s) be dopant material(s) (also referred to as guest material(s), emitter(s), or luminescent material(s)). The fourth compound(s) that fluoresces, in the second emitting layer, can be one(s) like the aforementioned second compound(s). The second compound(s) that fluoresces, in the first emitting layer, and the fourth compound(s) that fluoresces, in the second emitting layer, are mutually the same or different. The fifth compound, in the second emitting layer, can be one like the aforementioned third compound. The third compound, in the first emitting layer, and the fifth compound, in the second emitting layer, are mutually different.
Preferably, the first emitting layer contains a pyrene derivative, more preferably a pyrene derivative as a host material.
Preferably, the second emitting layer contains an anthracene derivative, more preferably an anthracene derivative as a host material.
More preferably, the first emitting layer contains a pyrene derivative as a host material, and the second emitting layer contains an anthracene derivative as a host material at the same time.
Preferably, the first and second emitting layers contain no phosphorescent material as a dopant material.
Preferably, furthermore, the first and second emitting layers contain no heavy metal complex and no phosphorescent rare earth metal complex. In this context, examples of heavy metal complexes include, for instance, iridium complexes, osmium complexes, and platinum complexes.
It is also preferred that the first and second emitting layers contain no metal complex.
The second compound(s) and the fourth compound(s) each independently represent one or more compounds selected from the group consisting of a compound represented by formula (3) below, a compound represented by formula (4) below, a compound represented by formula (5) below, a compound represented by formula (6) below, a compound represented by formula (7) below, a compound represented by formula (8) below, a compound represented by formula (9) below, and a compound represented by formula (10) below.
The following describes the compounds represented by formula (3).
In formula (3),
at least one combination of adjacent two or more of R301 to R310 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bound together;
at least one of R301 to R310 is a monovalent group represented by formula (31) below; and
R301 to R310 forming neither the monocyclic ring nor the fused ring and not being the monovalent group represented by formula (31) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In formula (31),
Ar301 and Ar302 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L301 to L303 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; and
* indicates the position of bonding with the pyrene ring in formula (3).
In a second compound, R901, R902, R903, R904, R905, R906, and R907 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R901s are present, the multiple R901s are mutually the same or different;
when multiple R902s are present, the multiple R902s are mutually the same or different;
when multiple R903s are present, the multiple R903s are mutually the same or different;
when multiple R904s are present, the multiple R904s are mutually the same or different;
when multiple R905s are present, the multiple R905s are mutually the same or different;
when multiple R906s are present, the multiple R906s are mutually the same or different; and
when multiple R907s are present, the multiple R907s are mutually the same or different.
In formula (3), it is preferred that two of R301 to R310 be groups represented by formula (31).
In an exemplary embodiment, the compounds represented by formula (3) are the compounds represented by formula (33) below.
In formula (33),
R311 to R316 each independently represent the same as when R301 to R310 in formula (3) are not monovalent groups represented by formula (31);
L311 to L316 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; and
Ar312, Ar313, Ar317, and Ar316 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In formula (31), it is preferred that L301 be a single bond, and it is preferred that L302 and L303 be single bonds.
In an exemplary embodiment, the compounds represented by formula (3) are represented by formula (34) or (35) below.
In formula (34),
R311 to R318 each independently represent the same as when R301 to R310 in formula (3) are not monovalent groups represented by formula (31);
L312, L313, L315, and L316 each independently represent the same as L312, L313, L315, and L316 in formula (33); and
Ar312, Ar313, Ar315, and Ar316 each independently represent the same as Ar312, Ar313, Ar315, and Ar316 in formula (33).
In formula (35),
R311 to R318 each independently represent the same as when R301 to R310 in formula (3) are not monovalent groups represented by formula (31); and
Ar312, Ar313, Ar31s, and Ar316 each independently represent the same as Ar312, Ar313, Ar31s, and Ar316 in formula (33).
In formula (31), it is preferred that at least one of Ar301 or Ar302 be a group represented by formula (36) below.
In formulae (33) to (35), it is preferred that at least one of Ar312 or Ar313 be a group represented by formula (36) below.
In formulae (33) to (35), it is preferred that at least one of Ar315 or Ar316 be a group represented by formula (36) below.
In formula (36),
X3 denotes an oxygen or sulfur atom;
at least one combination of adjacent two or more of R321 to R327 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
R321 to R327 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; and
* indicates the position of bonding with L302, L303, L312, L313, L315, or L316.
Preferably, X3 is an oxygen atom.
Preferably, at least one of R321 to R327 is: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In formula (31), it is preferred that Ar301 be a group represented by formula (36) and that Ar302 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In formulae (33) to (35), it is preferred that Ar312 be a group represented by formula (36) and that Ar313 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In formulae (33) to (35), it is preferred that Ar315 be a group represented by formula (36) and that Ar316 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compounds represented by formula (3) are represented by formula (37) below.
In formula (37),
R311 to R318 each independently represent the same when R301 to R310 in formula (3) are not monovalent groups represented by formula (31);
at least one combination of adjacent two or more of R321 to R327 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
at least one combination of adjacent two or more of R341 to R347 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R321 to R327 and R341 to R347 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; and
R331 to R335 and R351 to R355 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of compounds represented by formula (3) include, for instance, the following compounds.
The following describes the compounds represented by formula (4).
In formula (4),
the Zs each independently represent CRa or a nitrogen atom;
rings A1 and A2 each independently represent: a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms;
when multiple Ras are present, at least one combination of adjacent two or more of the multiple Ras are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
n21 and n22 each independently represent 0, 1, 2, 3, or 4;
when multiple Rbs are present, at least one combination of adjacent two or more of the multiple Rbs are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
when multiple Rcs are present, at least one combination of adjacent two or more of the multiple Rcs are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
Ra, Rb, and Rc not forming the monocyclic ring and not forming the fused ring each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
An “aromatic hydrocarbon ring” as ring A1 or A2 is structurally the same as a compound that is formed when hydrogen atom(s) is introduced into an “aryl group” as described above.
The ring atoms of an “aromatic hydrocarbon ring” as ring A1 or A2 include the two carbon atoms on the two-ring fused structure in the middle of formula (4).
Specific examples of the “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms” include a compound formed by introducing a hydrogen atom to the “aryl group” described in the specific example group G1.
A “heterocycle” as ring A1 or A2 is structurally the same as a compound that is formed when hydrogen atom(s) is introduced into a “heterocyclic group” as described above.
The ring atoms of a “heterocycle” as ring A1 or A2 include the two carbon atoms on the two-ring fused structure in the middle of formula (4).
Specific examples of the “substituted or unsubstituted heterocycle having 5 to 50 ring atoms” include a compound formed by introducing a hydrogen atom to the “heterocyclic group” described in the specific example group G2.
The Rb(s) is bonded to any of the carbon atoms forming an aromatic hydrocarbon ring as ring A1 or any of the atoms forming a heterocycle as ring A1.
The Rc(s) is bonded to any of the carbon atoms forming an aromatic hydrocarbon ring as ring A2 or any of the atoms forming a heterocycle as ring A2.
Preferably, at least one of Ra, Rb, or Rc is a group represented by formula (4a) below. More preferably, at least two are groups represented by formula (4a) below.
In formula (4a),
L401 is: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; and
Ar401 is: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; or a group represented by formula (4b) below.
In formula (4b),
L402 and L403 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms;
the combination of Ar402 and Ar403 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
Ar402 and Ar403 not forming the monocyclic ring and not forming the fused ring each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (4) are represented by formula (42) below.
In formula (42),
at least one combination of adjacent two or more of R401 to R411 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R401 to R411 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Preferably, at least one of R401 to R411 is a group represented by formula (4a). More preferably, at least two are groups represented by formula (4a).
Preferably, R404 and R411 are groups represented by formula (4a).
In an exemplary embodiment, the compounds represented by formula (4) are compounds that are formed when a structure represented by formula (4-1) or (4-2) below is bonded to their ring A1.
In an exemplary embodiment, furthermore, the compounds represented by formula (42) are compounds that are formed when a structure represented by formula (4-1) or (4-2) below is bonded to their ring to which R404 to R407 are bonded.
In formula (4-1), the two *s are each independently bonded to a ring carbon atom of an aromatic hydrocarbon ring or a ring atom of a heterocycle as ring A1 in formula (4) or any of R404 to R407 in formula (42);
the three *s in formula (4-2) are each independently bonded to a ring carbon atom of an aromatic hydrocarbon ring or a ring atom of a heterocycle as ring A1 in formula (4) or any of R404 to R407 in formula (42); at least one combination of adjacent two or more of R421 to R427 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
at least one combination of adjacent two or more of R431 to R438 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R421 to R427 and R431 to R438 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (4) are compounds represented by formula (41-3), (41-4), or (41-5) below.
In formulae (41-3), (41-4), and (41-5), ring A1 is as defined in formula (4);
R421 to R427 each independently represent the same as R421 to R427 in formula (4-1); and
R440 to R448 each independently represent the same as R401 to R411 in formula (42).
In an exemplary embodiment, a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms as ring A1 in formula (41-5) is: a substituted or unsubstituted naphthalene ring; or a substituted or unsubstituted fluorene ring.
In an exemplary embodiment, a substituted or unsubstituted heterocycle having 5 to 50 ring atoms as ring A1 in formula (41-5) is: a substituted or unsubstituted dibenzofuran ring; a substituted or unsubstituted carbazole ring; or a substituted or unsubstituted dibenzothiophene ring.
In an exemplary embodiment, the compounds represented by formula (4) or (42) are selected from the group consisting of the compounds represented by formulae (461) to (467) below.
In formulae (461), (462), (463), (464), (465), (466), and (467), R421 to R427 each independently represent the same as R421 to R427 in formula (4-1);
R431 to R438 each independently represent the same as R431 to R438 in formula (4-2);
R440 to R448 and R451 to R454 each independently represent the same as R401 to R411 in formula (42);
X4 is an oxygen atom, NR801, or C(R802)(R803);
R801, R802, and R803 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R801s are present, the multiple R801s are mutually the same or different;
when multiple R802s are present, the multiple R802s are mutually the same or different; and
when multiple R803s are present, the multiple R803s are mutually the same or different.
In an exemplary embodiment, at least one combination of adjacent two or more of R401 to R411 in a compound represented by formula (42) are bonded together to form a substituted or unsubstituted monocyclic ring or bonded together to form a substituted or unsubstituted fused ring. The following describes this exemplary embodiment in detail, with such compounds defined as compounds represented by formula (45).
The following describes the compounds represented by formula (45).
In formula (45),
two or more of combinations selected from the group consisting of a combination of R461 and R462, a combination of R462 and R463, a combination of R464 and R465, a combination of R465 and R466, a combination of R466 and R467, a combination of R468 and R469, a combination of R469 and R470, and a combination of R470 and R471 are mutually bonded to form a substituted or unsubstituted monocyclic ring or a substituted or unsubstituted fused ring.
However, the combination of R461 and R462 and the combination of R462 and R463; the combination of R464 and R465 and the combination of R465 and R466; the combination of R465 and R466 and the combination of R466 and R467; the combination of R468 and R469 and the combination of R469 and R470; and the combination of R469 and R470 and the combination of R470 and R471 do not form a ring at the same time.
At least two rings formed by R461 to R471 are mutually the same or different.
R461 to R471 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In formula (45), Rn and Rn+1 (where n indicates an integer selected from 461, 462, 464 to 466, and 468 to 470) are bonded together to form a substituted or unsubstituted monocyclic ring or substituted or unsubstituted fused ring in conjunction with the two ring carbon atoms to which Rn and Rn+1 are bonded. Preferably, the ring is formed by atoms selected from the group consisting of carbon, oxygen, sulfur, and nitrogen atoms. Preferably, the number of atoms in the ring is between 3 and 7, more preferably 5 or 6.
The number of such cyclic structures in a compound represented by formula (45) is, for example, two, three, or four. Each of the two or more cyclic structures may be present on the same benzene ring on the base skeleton in formula (45) or may be present on different benzene rings. For example, if the compound has three cyclic structures, each of the three benzene rings in formula (45) may have one of them.
Examples of such cyclic structures in a compound represented by formula (45) include, for instance, the structures represented by formulae (451) to (460) below.
In formulae (451) to (457),
each of the pairs *1 and *2, *3 and *4, *5 and *6, *7 and *8, *9 and *10, *11 and *12, and *13 and *14 represents the aforementioned two ring carbon atoms to which Rn and Rn+1 are bonded;
the ring carbon atom to which Rn is bonded can be either of the two represented by *1 and *2, *3 and *4, *5 and *6, *7 and *8, *9 and *10, *11 and *12, or *13 and *14;
X45 is C(R4512)(R4513), NR4514, an oxygen atom, or a sulfur atom;
at least one combination of adjacent two or more of R4501 to R4506 and R4512 to R4513 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R4501 to R4514 not forming the monocyclic ring and not forming the fused ring each independently represent the same as R461 to R471 in formula (45).
In formulae (458) to (460),
each of the pairs *1 and *2 and *3 and *4 represents the aforementioned two ring carbon atoms to which Rn and Rn+1 are bonded;
the ring carbon atom to which Rn is bonded can be either of the two represented by *1 and *2 or *3 and *4;
X45 is C(R4512)(R4513), NR4514, an oxygen atom, or a sulfur atom;
at least one combination of adjacent two or more of R4512 to R4513 and R4515 to R4525 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R4512 to R4513, R4515 to R4521, and R4522 to R4525 not forming the monocyclic ring and not forming the fused ring and R4514 each independently represent the same as R461 to R471 in formula (45).
In formula (45), it is preferred that at least one of R462, R464, R465, R470, or R471 (preferably at least one of R462, R465, or R470, more preferably R462) be a group not forming the cyclic structure.
Preferably, (i) the substituent(s) in any substituted ring structure(s) formed by Rn and Rn+1 in formula (45); (ii) R461 to R471 not forming the cyclic structure in formula (45); and (iii) R4501 to R4514 and R4515 to R4525 in formulae (451) to (460) each independently represent any of: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —N(R906)(R907); a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; or a group selected from the group consisting of the groups represented by formulae (461) to (464) below.
In formulae (461) to (464),
the Rds each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
X46 is C(R801)(R802), NR803, an oxygen atom, or a sulfur atom;
R801, R802, and R803 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R801s are present, the multiple R801s are mutually the same or different;
when multiple R802s are present, the multiple R802s are mutually the same or different;
when multiple R803s are present, the multiple R803s are mutually the same or different;
p1 is 5;
p2 is 4;
p3 is 3;
p4 is 7; and
the *s in formulae (461) to (464) each independently indicate a position of bonding with the cyclic structure.
In the second compound, R901 to R907 are as defined above.
In an exemplary embodiment, the compounds represented by formula (45) are represented by any of formulae (45-1) to (45-6) below.
In formulae (45-1) to (45-6),
rings d to i each independently represent a substituted or unsubstituted monocyclic ring or substituted or unsubstituted fused ring; and
R461 to R471 each independently represent the same as R461 to R471 in formula (45).
In an exemplary embodiment, the compounds represented by formula (45) are represented by any of formulae (45-7) to (45-12) below.
In formulae (45-7) to (45-12),
rings d to f, k, and j each independently represent a substituted or unsubstituted monocyclic ring or substituted or unsubstituted fused ring; and
R461 to R471 each independently represent the same as R461 to R471 in formula (45).
In an exemplary embodiment, the compounds represented by formula (45) are represented by any of formulae (45-13) to (45-21) below.
In formulae (45-13) to (45-21),
rings d to k each independently represent a substituted or unsubstituted monocyclic ring or substituted or unsubstituted fused ring; and
R461 to R471 each independently represent the same as R461 to R471 in formula (45).
Examples of substituents if ring g or h has substituent(s) include: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; a group represented by formula (461); a group represented by formula (463); and a group represented by formula (464).
In an exemplary embodiment, the compounds represented by formula (45) are represented by any of formulae (45-22) to (45-25).
In formulae (45-22) to (45-25),
X46 and X47 each independently represent C(R801)(R802), NR803, an oxygen atom, or a sulfur atom; and
R461 to R471 and R481 to R488 each independently represent the same as R461 to R471 in formula (45).
R801, R802, and R803 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R801s are present, the multiple R801s are mutually the same or different;
when multiple R802s are present, the multiple R802s are mutually the same or different; and
when multiple R803s are present, the multiple R803s are mutually the same or different.
In an exemplary embodiment, the compounds represented by formula (45) are represented by formula (45-26) below.
In formula (45-26),
X46 is C(R801)(R802), NR803, an oxygen atom, or a sulfur atom; and
R463, R464, R467, R468, R471, and R481 to R492 each independently represent the same as R461 to R471 in formula (45).
R801, R802, and R803 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R801s are present, the multiple R801s are mutually the same or different;
when multiple R802s are present, the multiple R802s are mutually the same or different; and
when multiple R803s are present, the multiple R803s are mutually the same or different.
Specific examples of compounds represented by formula (4) include, for instance, the following compounds. In these specific examples, Ph denotes a phenyl group, and D denotes a deuterium atom.
The following describes the compounds represented by formula (5). The compounds represented by formula (5) are compounds that correspond to the compounds represented by formula (41-3), described above.
In formula (5),
at least one combination of adjacent two or more of R501 to R507 and R511 to R517 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R501 to R507 and R511 to R517 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
R521 and R522 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
“A combination of adjacent two or more of R501 to R507 and R511 to R517” refers to, for instance, a combination of R501 and R502, a combination of R502 and R503, a combination of R503 and R504, a combination of R505 and R506, a combination of R506 and R507, and a combination of R501, R502, and R503.
In an exemplary embodiment, at least one of R501 to R507 or R511 to R517, preferably two, is a group represented by —N(R906)(R907).
In an exemplary embodiment, R501 to R507 and R511 to R517 each independently represent: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (5) are the compounds represented by formula (52) below.
In formula (52),
at least one combination of adjacent two or more of R531 to R534 and R541 to R544 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R531 to R534, R541 to R544 not forming the monocyclic ring and not forming the fused ring, and R551 and R552 each independently represent: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; and
R561 to R564 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (5) are the compounds represented by formula (53) below.
In formula (53), R551, R552, and R561 to R564 each independently represent the same as R551, R552, and R561 to R564 in formula (52).
In an exemplary embodiment, R561 to R564 in formulae (52) and (53) each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably, a phenyl group).
In an exemplary embodiment, R521 and R522 in formula (5) and R551 and R552 in formulae (52) and (53) are hydrogen atoms.
In an exemplary embodiment, a substituent for “substituted or unsubstituted” group in formulae (5), (52) and (53) is: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of compounds represented by formula (5) include, for instance, the following compounds.
The following describes the compounds represented by formula (6).
In formula (6),
rings a, b, and c each independently represent: a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms;
R601 and R602 are each independently bonded to ring a, ring b or ring c to form a substituted or unsubstituted heterocycle, or not bonded to form no substituted or unsubstituted heterocycle; and
R601 and R602 not forming the substituted or unsubstituted heterocycle each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Rings a, b, and c are each a ring fused to the two-ring fused structure, formed by a boron and two nitrogen atoms, in the middle of formula (6) (each being a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms).
An “aromatic hydrocarbon ring” as ring a, b, or c is structurally the same as a compound that is formed when hydrogen atom(s) is introduced into an “aryl group” as described above.
The ring atoms of an “aromatic hydrocarbon ring” as ring a include the three carbon atoms on the two-ring fused structure in the middle of formula (6).
The ring atoms of an “aromatic hydrocarbon ring” as ring b or c include the two carbon atoms on the two-ring fused structure in the middle of formula (6).
Specific examples of the “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms” include a compound formed by introducing a hydrogen atom to the “aryl group” described in the specific example group G1.
A “heterocycle” as ring a, b, or c is structurally the same as a compound that is formed when hydrogen atom(s) is introduced into a “heterocyclic group” as described above.
The ring atoms of a “heterocycle” as ring a include the three carbon atoms on the two-ring fused structure in the middle of formula (6). A “heterocycle” as ring b or c include the two carbon atoms on the two-ring fused structure in the middle of formula (6). Specific examples of the “substituted or unsubstituted heterocycle having 5 to 50 ring atoms” include a compound formed by introducing a hydrogen atom to the “heterocyclic group” described in the specific example group G2.
R601 and R602 are optionally each independently bonded with ring a, ring b, or ring c to form a substituted or unsubstituted heterocycle. A heterocycle in that case includes the nitrogen atom on the two-ring fused structure in the middle of formula (6). A heterocycle in that case may include heteroatoms other than the nitrogen atom. The binding of R601 or R602 to ring a, b, or c specifically means an atom as a component of ring a, b, or c and that as a component of R601 or R602 are bonded together. For example, R601 may bind to ring a to form a nitrogen-containing heterocycle with two (or three or more) fused rings in which ring(s) including R901 and ring a are fused together. Specific examples of the “substituted or unsubstituted heterocycle having 5 to 50 ring atoms” include a compound formed by introducing a hydrogen atom to the “heterocyclic group” described in the specific example group G2.
The same is true when R601 is bonded to ring b, when R602 is bonded to ring a, or when R602 is bonded to ring c, too.
In an exemplary embodiment, rings a, b, and c in formula (6) each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms.
In an exemplary embodiment, rings a, b, and c in formula (6) each independently represent a substituted or unsubstituted benzene or naphthalene ring.
In an exemplary embodiment, R901 and R602 in formula (6) each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compounds represented by formula (6) are the compounds represented by formula (62) below.
In formula (62),
R601A is bonded with at least one of R611 or R621 to form a substituted or unsubstituted heterocycle, or not bonded to form no substituted or unsubstituted heterocycle;
R602A is bonded with at least one of R613 or R614 to form a substituted or unsubstituted heterocycle, or not bonded to form no substituted or unsubstituted heterocycle;
R601A and R602A not forming the substituted or unsubstituted heterocycle each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
at least one combination of adjacent two or more of R611 to R621 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R611 to R621 not forming the substituted or unsubstituted heterocycle, not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
R601A and R602A in formula (62) are groups corresponding to R601 and R602, respectively, in formula (6).
For example, R601A and R611 may be bonded together to form a nitrogen-containing heterocycle with two (or three or more) fused rings in which ring(s) including them and the benzene ring corresponding to ring a are fused together. Specific examples of such nitrogen-containing heterocycles include compounds corresponding to the nitrogen-containing heterocyclic groups with two or more fused rings in specific example group G2. The same is true when R601A and R621 are bonded together, when R602A and R613 are bonded together, or when R602A and R614 are bonded together, too.
It may be that at least one combination of adjacent two or more of R611 to R621 are: bonded together to form a substituted or unsubstituted monocyclic ring; or bonded together to form a substituted or unsubstituted fused ring.
For example, R611 and R612 may be bonded together to form a structure in which a benzene, indole, pyrrole, benzofuran, or benzothiophene ring, for example, is fused to the six-membered ring to which the Rs are bonded. The resulting fused ring is a naphthalene, carbazole, indole, dibenzofuran, or dibenzothiophene ring.
In an exemplary embodiment, R611 to R621 not contributing to ring formation each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation each independently represent: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation each independently represent: a hydrogen atom; or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, R611 to R621 not contributing to ring formation each independently represent: a hydrogen atom; or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; and at least one of R611 to R621 is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, the compounds represented by formula (62) are the compounds represented by formula (63) below.
In formula (63),
R631 is bonded with R646 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle;
R633 is bonded with R647 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle;
R634 is bonded with R651 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle;
R641 is bonded with R642 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle; at least one combination of adjacent two or more of R631 to R651 are mutually bonded to form a substituted or unsubstituted monocyclic ring, mutually bonded to form a substituted or unsubstituted fused ring, or not mutually bonded; and
R631 to R651 not forming the substituted or unsubstituted heterocycle, not forming the monocyclic ring, and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
R631 are optionally mutually bonded with R646 to form a substituted or unsubstituted heterocycle. For example, R631 and R646 may be bonded together to form a nitrogen-containing heterocycle with three or more fused rings in which the benzene ring to which R646 is bonded, the ring including N, and the benzene ring corresponding to ring a are fused together. Specific examples of such nitrogen-containing heterocycles include compounds corresponding to the nitrogen-containing heterocyclic groups with three or more fused rings in specific example group G2. The same is true when R633 and R647 are bonded together, when R634 and R651 are bonded together, or when R641 and R642 are bonded together, too.
In an exemplary embodiment, R631 to R651 not contributing to ring formation each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation each independently represent: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation each independently represent: a hydrogen atom; or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, R631 to R651 not contributing to ring formation each independently represent: a hydrogen atom; or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; and
at least one of R631 to R651 is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, the compounds represented by formula (63) are the compounds represented by formula (63A) below.
In formula (63A),
R661 is: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; and
R662 to R665 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R661 to R665 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R661 to R665 each independently represent a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, the compounds represented by formula (63) are the compounds represented by formula (63B) below.
In formula (63B),
R671 and R672 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —N(R906)(R907); or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; and
R673 to R675 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —N(R906)(R907); or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compounds represented by formula (63) are the compounds represented by formula (63B′) below.
In formula (63B′), R672 to R675 each independently represent the same as R672 to R675 in formula (63B).
In an exemplary embodiment, at least one of R671 to R675 is: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —N(R906)(R907); or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R672 is: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a group represented by —N(R906)(R907); or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; and
R671 and R673 to R675 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a group represented by —N(R906)(R907); or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compounds represented by formula (63) are the compounds represented by formula (63C) below.
In formula (63C),
R681 and R682 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
R683 to R686 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, the compounds represented by formula (63) are the compounds represented by formula (63C′) below.
In formula (63C′), R683 to R686 each independently represent the same as R683 to R686 in formula (63C).
In an exemplary embodiment, R681 to R686 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R681 to R686 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
To make a compound represented by formula (6), an intermediate is first produced by binding rings a, b, and c together using linking groups (a group including N—R601 and that including N—R602) (first reaction), and then binding rings a, b, and c using a linking group (including a boron atom) will give the final product (second reaction). The first reaction can be amination, such as the Buchwald-Hartwig amination. The second reaction can be, for example, heterogeneously catalyzed tandem Friedel-Crafts reactions.
The following are specific examples of compounds represented by formula (6). It should be noted that these are given for illustrative purposes only; the following specific examples are not the only possible forms of compounds represented by formula (6).
The following describes the compounds represented by formula (7).
In formula (7),
ring r is a ring represented by formula (72) or (73) and fused with adjacent ring(s) at any position(s);
rings q and s each independently represent a ring represented by formula (74) fused with adjacent ring(s) at any position(s);
rings p and t each independently represent a structure represented by formula (75) or (76) fused with adjacent ring(s) at any position(s); and
X7 is an oxygen atom, a sulfur atom, or NR702.
When multiple R701s are present, the multiple R701s adjacent to one another are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
R701 and R702 not forming the monocyclic ring and not forming the fused ring each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
Ar701 and Ar702 each independently represent: a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L701 is: a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenylene group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynylene group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkylene group having 3 to 50 ring carbon atoms; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
m1 is 0, 1, or 2;
m2 is 0, 1, 2, 3, or 4;
each m3 independently represents 0, 1, 2, or 3;
each m4 independently represents 0, 1, 2, 3, 4, or 5;
when multiple R701s are present, the multiple R701s are mutually the same or different;
when multiple X7s are present, the multiple X7s are mutually the same or different;
when multiple R702s are present, the multiple R702s are mutually the same or different;
when multiple Ar701s are present, the multiple Ar701s are mutually the same or different;
when multiple Ar702s are present, the multiple Ar702s are mutually the same or different; and
when multiple L701s are present, the multiple L701s are mutually the same or different.
In formula (7), each of rings p, q, r, s, and t is fused to the adjacent ring(s), sharing two carbon atoms. The position and direction of fusion are not critical; the rings can be fused at any position and in any direction.
In an exemplary embodiment, in formula (72) or (73), as ring r, m1=0, or m2=0 is satisfied.
In an exemplary embodiment, the compounds represented by formula (7) are represented by any of formulae (71-1) to (71-6) below.
In formulae (71-1) to (71-6), R701, X7, Ar701, Ar702, L701, m1, and m3 represent the same as R701, X7, Ar701, Ar702, L701, m1, and m3, respectively, in formula (7).
In an exemplary embodiment, the compounds represented by formula (7) are represented by any of formulae (71-11) to (71-13) below.
In formulae (71-11) to (71-13), R701, X7, Ar701, Ar702, L701, m1, m3, and m4 represent the same as R701, X7, Ar701, Ar702, L701, m1, m3, and m4, respectively, in formula (7).
In an exemplary embodiment, the compounds represented by formula (7) are represented by any of formulae (71-21) to (71-25) below.
In formulae (71-21) to (71-25), R701, X7, Ar701, Ar702, L701, m1, and m4 represent the same as R701, X7, Ar701, Ar702, L701, m1, and m4, respectively, in formula (7).
In an exemplary embodiment, the compounds represented by formula (7) are represented by any of formulae (71-31) to (71-33) below.
In formulae (71-31) to (71-33), R701, X7, Ar701, Ar702, L701, and m2 to m4 represent the same as R701, X7, Ar701, Ar702, L701, and m2 to m4, respectively, in formula (7).
In an exemplary embodiment, Ar701 and Ar702 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, one of Ar701 and Ar702 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and the other is a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of compounds represented by formula (7) include, for instance, the following compounds.
The following describes the compounds represented by formula (8).
In formula (8),
at least one combination of R801 and R802, R802 and R803, or R803 and R804 are bonded together to form a divalent group represented by formula (82) below or are not bonded together; and
at least one combination of R805 and R806, R806 and R807, or R807 and R808 are bonded together to form a divalent group represented by formula (83) below or are not bonded together.
At least one of R801 to R804 not forming the divalent group represented by formula (82) or R811 to R814 is a monovalent group represented by formula (84) below;
at least one of R805 to R808 not forming the divalent group represented by formula (83) or R821 to R824 is a monovalent group represented by formula (84) below;
X8 is CR81R82, an oxygen atom, a sulfur atom, or NR808; the combination of R81 and R82 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R801 to R808 not forming the divalent groups represented by the formulae (82) and (83) and not being the monovalent group represented by the formula (84), R811 to R814 and R821 to R824 not being the monovalent group represented by the formula (84), R81 and R82 not forming the substituted or unsubstituted monocyclic ring and not forming the substituted or unsubstituted fused ring, and R808 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In formula (84),
Ar811 and Ar802 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L801 to L803 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; or a divalent linking group formed by two to four groups bonded together, each of the two to four selected from the group consisting of a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms and a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; and
* in formula (84) indicates the position of bonding with the cyclic structure represented by formula (8) or the group represented by formula (82) or (83).
It is also preferred that at least one combination of R801 and R802, R802 and R803, or R803 and R804 be bonded together while R805 and R806, R806 and R807, and R807 and R808 are not bonded together.
It is also preferred that R801 and R802, R802 and R803, and R803 and R804 be not bonded together while at least one combination of R805 and R806, R806 and R807, or R807 and R808 are bonded together.
It is also preferred that at least one combination of R801 and R802, R802 and R803, or R803 and R804 be bonded together to form a divalent group represented by formula (82) while at least one combination of R805 and R806, R806 and R807, or R807 and R808 are bonded together to form a divalent group represented by formula (83).
In formula (8), the position at which the divalent group represented by formula (82) or that represented by formula (83) is formed is not critical; the group can be formed at any possible position from R801 to R808.
In an exemplary embodiment, the compounds represented by formula (8) are represented by any of formulae (81A-1) to (81A-3) below.
In formulae (81A-1) to (81A-3),
X8 represents the same as X8 in formula (8);
at least one of R803, R804, or R811 to R814 in formula (81A-1) is a monovalent group represented by formula (84);
at least one of R801, R804, or R811 to R814 in formula (81A-2) is a monovalent group represented by formula (84);
at least one of R801, R802, or R811 to R814 in formula (81A-3) is a monovalent group represented by formula (84);
at least one of R805 to R808 in formulae (81A-1) to (81A-3) is a monovalent group represented by formula (84); and
R801 to R808 and R811 to R814 not being the monovalent group represented by formula (84) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (8) are represented by any of formulae (81-1) to (81-6) below.
In formulae (81-1) to (81-6),
X8 represents the same as X8 in formula (8);
at least two of R81 to R824 are monovalent groups represented by formula (84); and
R801 to R824 not being the monovalent group represented by formula (84) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (8) are represented by any of formulae (81-7) to (81-18) below.
In formulae (81-7) to (81-18),
X8 represents the same as X8 in formula (8);
the *s are single bonds bonded to the monovalent groups represented by formula (84); and
R801 to R824 each independently represent the same as when R801 to R824 in formulae (81-1) to (81-6) are not monovalent groups represented by formula (84).
Preferably, R801 to R808 not forming the divalent group represented by formula (82) or (83) and not being the monovalent group represented by formula (84) and R811 to R814 and R821 to R824 not being the monovalent group represented by formula (84) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Preferably, the monovalent groups represented by formula (84) are represented by formula (85) or (86) below.
In formula (85),
R831 to R840 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; and
* in formula (85) represents the same as * in formula (84).
In formula (86),
Ar801, L801, and L803 represent the same as Ar801, L801, and L803 in formula (84); and HAr801 is a structure represented by formula (87) below.
In formula (87),
X81 is an oxygen or sulfur atom;
one of R841 to R848 is a single bond bonded to L803; and
R841 to R848 not being the single bond each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
Specific examples of compounds represented by formula (8) include compounds mentioned in WO 2014/104144. Besides them, the following, for instance, are also specific examples of such compounds.
The following describes the compounds represented by formula (9).
In formula (9),
rings A91 and A92 each independently represent: a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms; and one or more rings selected from the group consisting of rings A91 and A92 are bonded to the *s in a structure represented by formula (92) below.
In formula (92),
ring A93 is: a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms;
X9 is NR93, C(R94)(R95), Si(R96)(R97), Ge(R98)(R99), an oxygen atom, a sulfur atom, or a selenium atom;
R91 and R92 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together; and
R91 and R92 not forming the monocyclic ring or the fused ring and R93 to R99 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
One or more rings selected from the group consisting of rings A91 and A92 are bonded to the *s in a structure represented by formula (92). That is, in an exemplary embodiment, ring carbon atoms of the aromatic hydrocarbon ring as ring A91 or ring atoms of the heterocycle as that ring are bonded to the *s in a structure represented by formula (92). In an exemplary embodiment, furthermore, ring carbon atoms of the aromatic hydrocarbon ring as ring A92 or ring atoms of the heterocycle as that ring are bonded to the *s in a structure represented by formula (92).
In an exemplary embodiment, a group represented by formula (93) below is bonded to one or both of rings A91 and A92.
In formula (93),
Ar91 and Ar92 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L91 to L93 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms; a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; or a divalent linking group formed by two to four groups bonded together, each of the two to four selected from the group consisting of a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms and a substituted or unsubstituted divalent heterocyclic group having 5 to 30 ring atoms; and
* in formula (93) indicates the position of bonding with either one of ring A91 or A92.
In an exemplary embodiment, ring carbon atoms of the aromatic hydrocarbon ring as ring A92 or ring atoms of the heterocycle as that ring are bonded to the *s in a structure represented by formula (92), as well as ring A91.
In that case, the structures represented by formula (92) may be mutually the same or different.
In an exemplary embodiment, R91 and R92 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, R91 and R92 are bonded together to form a fluorene structure.
In an exemplary embodiment, rings A91 and A92 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, such as a substituted or unsubstituted benzene ring.
In an exemplary embodiment, ring A93 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, such as a substituted or unsubstituted benzene ring.
In an exemplary embodiment, X9 is an oxygen or sulfur atom.
Specific examples of compounds represented by formula (9) include, for instance, the following compounds.
The following describes the compounds represented by formula (10).
In formula (10),
ring Ax1 is a ring represented by formula (10a) fused with adjacent ring(s) at any position(s);
ring Ax2 is a ring represented by formula (10b) fused with adjacent ring(s) at any position(s);
the two *s in formula (10b) are bonded to any positions of ring Ax3;
XA and XB each independently represent C(R1003)(R1004), Si(R1005)(R1006), an oxygen atom, or a sulfur atom;
ring Ax3 is: a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocycle having 5 to 50 ring atoms;
Ar1001 is: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
R1101 to R1006 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
mx1 is 3; mx2 is 2;
the multiple R1001s are mutually the same or different;
the multiple R1002s are mutually the same or different;
ax is 0, 1, or 2;
if ax is 0 or 1, the structures in the brackets indicated by “3-ax” are mutually the same or different; and
if ax is 2, the multiple Ar1001s are mutually the same or different.
In an exemplary embodiment, Ar1001 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In an exemplary embodiment, ring Ax3 is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, such as a substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, or substituted or unsubstituted anthracene ring.
In an exemplary embodiment, R1003 and R1004 each independently represent a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In an exemplary embodiment, ax is 1.
Specific examples of compounds represented by formula (10) include, for instance, the following compounds.
In an exemplary embodiment, the emitting layer contains, as the second compound(s), one or more compounds selected from the group consisting of: the compounds represented by formula (4); the compounds represented by formula (5); the compounds represented by formula (7); the compounds represented by formula (8); the compounds represented by formula (9); and the compounds represented by formula (63a) below.
In formula (63a),
R631 is bonded with R646 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle,
R633 is bonded with R647 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle,
R634 is bonded with R651 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle,
R641 is bonded with R642 to form a substituted or unsubstituted heterocycle, or not bonded therewith to form no substituted or unsubstituted heterocycle, at least one combination of adjacent two or more of R631 to R651 are mutually bonded to form a substituted or unsubstituted monocyclic ring, mutually bonded to form a substituted or unsubstituted fused ring, or not mutually bonded,
R631 to R651 not forming the substituted or unsubstituted heterocycle, not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
at least one of R631 to R651 not forming the substituted or unsubstituted heterocycle, not forming the monocyclic ring and not forming the fused ring is: a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, the compounds represented by formula (4) are the compounds represented by formula (41-3), (41-4), or (41-5), and ring A1 in formula (41-5) is a substituted or unsubstituted fused aromatic hydrocarbon ring system having 10 to 50 ring carbon atoms or substituted or unsubstituted fused heterocyclic system having 8 to 50 ring atoms.
In an exemplary embodiment, in formulae (41-3), (41-4), and (41-5), the substituted or unsubstituted fused aromatic hydrocarbon ring system having 10 to 50 ring carbon atoms is: a substituted or unsubstituted naphthalene ring; a substituted or unsubstituted anthracene ring; or a substituted or unsubstituted fluorene ring; and
the substituted or unsubstituted fused heterocyclic system having 8 to 50 ring atoms is: a substituted or unsubstituted dibenzofuran ring; a substituted or unsubstituted carbazole ring; or a substituted or unsubstituted dibenzothiophene ring.
In an exemplary embodiment, in formula (41-3), (41-4), or (41-5), the substituted or unsubstituted fused aromatic hydrocarbon ring system having 10 to 50 ring carbon atoms is: a substituted or unsubstituted naphthalene ring; or a substituted or unsubstituted fluorene ring; and
the substituted or unsubstituted fused heterocyclic system having 8 to 50 ring atoms is: a substituted or unsubstituted dibenzofuran ring; a substituted or unsubstituted carbazole ring; or a substituted or unsubstituted dibenzothiophene ring.
In an exemplary embodiment, the compounds represented by formula (4) are selected from the group consisting of: the compounds represented by formula (461) below; the compounds represented by formula (462) below; the compounds represented by formula (463) below; the compounds represented by formula (464) below; the compounds represented by formula (465) below; the compounds represented by formula (466) below; and the compounds represented by formula (467) below.
In formulae (461) to (467),
at least one combination of adjacent two or more of R421 to R427, R431 to 5 R436, R440 to R448, and R441 to R44 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
R437, R438, and R421 to R427, R431 to R436, R440 to R448, and R451 to R454 not forming the monocyclic ring and not forming the fused ring each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R900)(R900); a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
X4 is an oxygen atom, NR801, or C(R802)(R803);
R801, R802, and R803 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
when multiple R801s are present, the multiple R801s are mutually the same or different;
when multiple R802s are present, the multiple R802s are mutually the same or different; and
when multiple R803s are present, the multiple R803s are mutually the same or different.
In an exemplary embodiment, R421 to R427 and R440 to R448 each independently represent: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, R421 to R427 and R440 to R447 are each independently selected from the group consisting of: a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms; and a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In an exemplary embodiment, the compounds represented by formula (41-3) are the compounds represented by formula (41-3-1) below.
In formula (41-3-1), R423, R425, R426, R442, R444, and R445 each independently represent the same as R423, R425, R426, R442, R444, and R445 in formula (41-3).
In an exemplary embodiment, the compounds represented by formula (41-3) are the compounds represented by formula (41-3-2) below.
In formula (41-3-2), R421 to R427 and R440 to R448 each independently represent the same as R421 to R427 and R440 to R448 in formula (41-3); and
at least one of R421 to R427 or R440 to R446 is a group represented by —N(R906)(R907).
In an exemplary embodiment, any two of R421 to R427 and R440 to R446 in formula (41-3-2) are groups represented by —N(R906)(R907).
In an exemplary embodiment, the compounds represented by (41-3-2) are the compounds represented by formula (41-3-3) below.
In formula (41-3-3), R421 to R424, R440 to R443, R447, and R448 each independently represent the same as R421 to R424, R440 to R443, R447, and R448 in formula (41-3); and
RA, RB, RC, and RD each independently represent: a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In an exemplary embodiment, the compounds represented by formula (41-3-3) are the compounds represented by formula (41-3-4) below.
In formula (41-3-4), R447, R448, RA, RB, RC, and RD each independently represent the same as R447, R448, RA, RB, RC, and RD in formula (41-3-3).
In an exemplary embodiment, RA, RB, RC, and RD each independently represent a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms.
In an exemplary embodiment, RA, RB, RC, and RD each independently represent a substituted or unsubstituted phenyl group.
In an exemplary embodiment, R447 and R448 are hydrogen atoms.
In an exemplary embodiment, a substituent for “substituted or unsubstituted” group in each of the formulae is: an unsubstituted alkyl group having 1 to 50 carbon atoms; an unsubstituted alkenyl group having 2 to 50 carbon atoms; an unsubstituted alkynyl group having 2 to 50 carbon atoms; an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; —Si(R901a)(R902a)(R903a); —O—(R904a); —S—(R905a); —N(R906a)(R907a); a halogen atom; a cyano group; a nitro group; an unsubstituted aryl group having 6 to 50 ring carbon atoms; or an unsubstituted heterocyclic group having 5 to 50 ring atoms;
R901a to R907a each independently represent: a hydrogen atom; an unsubstituted alkyl group having 1 to 50 carbon atoms; an unsubstituted aryl group having 6 to 50 ring carbon atoms; or an unsubstituted heterocyclic group having 5 to 50 ring atoms;
when two or more R901as are present, the two or more R901as are mutually the same or different;
when two or more R902as are present, the two or more R902as are mutually the same or different;
when two or more R903as are present, the two or more R903as are mutually the same or different;
when two or more R904as are present, the two or more R904as are mutually the same or different;
when two or more R905as are present, the two or more R905as are mutually the same or different;
when two or more R906as are present, the two or more R906as are mutually the same or different; and
when two or more R907as are present, the two or more R907as are mutually the same or different.
In an exemplary embodiment, a substituent for “substituted or unsubstituted” group in each of the formulae is: an unsubstituted alkyl group having 1 to 50 carbon atoms; an unsubstituted aryl group having 6 to 50 ring carbon atoms; or an unsubstituted heterocyclic group having 5 to 50 ring atoms.
In an exemplary embodiment, a substituent for “substituted or unsubstituted” group in each of the formulae is: an unsubstituted alkyl group having 1 to 18 carbon atoms; an unsubstituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that the second compound(s) be compound(s) that exhibits light emission with a maximum peak wavelength in a range from 430 nm to 480 nm.
The measurement of the maximum peak wavelength of a compound is as follows. A 10−6 mol/L or more and 10−5 mol/L or less solution of the compound of interest in toluene is prepared and put into a quartz cell, and the emission spectrum of this sample is measured at room temperature (300 K) (the ordinate axis, luminous intensity; the abscissa axis, wavelength). The emission spectrum can be measured using Hitachi High-Tech Science Corporation's spectrophotometer (model: F-7000), although the system for measuring the emission spectrum does not need to be this.
In the emission spectrum, the peak wavelength of the emission spectrum at which the luminous intensity peaks is defined as the maximum emission peak wavelength. It should be noted that the maximum peak wavelength for fluorescence may herein be referred to as the maximum fluorescence peak wavelength (FL-peak).
In the second compound(s), it is preferred that all groups described as “substituted or unsubstituted” be “unsubstituted” groups
In the organic EL device according to this exemplary embodiment, examples of third and fifth compounds as host materials include, for instance, heterocyclic compounds and fused aromatic compounds. Examples of preferred fused aromatic compounds include, for instance, anthracene derivatives, pyrene derivatives, chrysene derivatives, and naphthacene derivatives.
In the organic EL device according to this exemplary embodiment, it is also preferred that the third compound be a compound represented by formula (1). In that case, the compound represented by formula (1) as the first compound, contained in the first hole transporting layer, and that as the third compound, contained in the emitting layer, are mutually the same or different.
It is also preferred that a third compound in a first emitting layer be a compound represented by formula (1) while a fifth compound in a second emitting layer is not. In that case, the compound represented by formula (1) as the first compound, contained in the first hole transporting layer, and that as the third compound, contained in the first emitting layer, are mutually the same or different.
In the organic EL device according to this exemplary embodiment, it is also preferred that the third compound is a compound represented by formula (2) below.
It is also preferred that a fifth compound in a second emitting layer be a compound represented by formula (2) below while a third compound in a first emitting layer is not.
It is also preferred that a third compound in a first emitting layer be a compound represented by formula (1) while a fifth compound in a second emitting layer is a compound represented by formula (2) below.
In formula (2),
R201 to R208 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L201 and L202 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms; and Ar201 and Ar202 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In a third compound according to this exemplary embodiment, R901, R902, R903, R904, R905, R905, R907, R801, and R802 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
when multiple R901s are present, the multiple R901s are mutually the same or different;
when multiple R902s are present, the multiple R902s are mutually the same or different;
when multiple R903s are present, the multiple R903s are mutually the same or different;
when multiple R904s are present, the multiple R904s are mutually the same or different;
when multiple R905s are present, the multiple R905s are mutually the same or different;
when multiple R906s are present, the multiple R906s are mutually the same or different;
when multiple R907s are present, the multiple R907s are mutually the same or different;
when multiple R801s are present, the multiple R801s are mutually the same or different; and
when multiple R802s are present, the multiple R802s are mutually the same or different.
In the organic EL device according to this exemplary embodiment, it is preferred that
R201 to R208 each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; a group represented by —Si(R901)(R902)(R903); a group represented by —O—(R904); a group represented by —S—(R905); a group represented by —N(R906)(R907); a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms; a group represented by —C(═O)R801; a group represented by —COOR802; a halogen atom; a cyano group; or a nitro group;
L201 and L202 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms; and
Ar201 and Ar202 each independently represent: a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that
L201 and L202 each independently represent: a single bond; or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; and
Ar201 and Ar202 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that Ar201 and Ar202 each independently represent: a phenyl group, a naphthyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a diphenylfluorenyl group, a dimethylfluorenyl group, a benzodiphenylfluorenyl group, a benzodimethylfluorenyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthobenzofuranyl group, or a naphthobenzothienyl group.
In the organic EL device according to this exemplary embodiment, it is preferred that the third compound represented by formula (2) be a compound represented by formula (201), (202), (203), (204), (205), (206), (207), (208), (209), or (210) below.
In formulae (201) to (210),
L201 and Ar201 represent the same as L201 and Ar201 in formula (2); and
R201 to R208 each independently represent the same as R201 to R208 in formula (2).
It is also preferred that the third compound represented by formula (2) be a compound represented by formula (221), (222), (223), (224), (225), (226), (227), (228), or (229) below.
In formulae (221), (222), (223), (224), (225), (226), (227), (228), and (229),
R201 and R203 to R208 each independently represent the same as R201 and R203 to R208 in formula (2);
L201 and Ar201 represent the same as L201 and Ar201, respectively, in formula (2);
L203 represents the same as L201 in formula (2);
L203 and L201 are mutually the same or different;
Ar203 represents the same as Ar201 in formula (2); and
Ar203 and Ar201 are mutually the same or different.
It is also preferred that the third compound represented by formula (2) be a compound represented by formula (241), (242), (243), (244), (245), (246), (247), (248), or (249) below.
In formulae (241), (242), (243), (244), (245), (246), (247), (248), and (249),
R201, R202 and R204 to R208 each independently represent the same as R201, R202 and R204 to R208 in formula (2);
L201 and Ar201 represent the same as L201 and Ar201, respectively, in formula (2);
L203 represents the same as L201 in formula (2);
L203 and L201 are mutually the same or different;
Ar203 represents the same as Ar201 in formula (2); and
Ar203 and Ar201 are mutually the same or different.
Preferably, in the third compound represented by formula (2), R201 to R208 not being the group represented by formula (21) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a group represented by —Si(R901)(R902)(R903).
Preferably, L101 is: a single bond; or an unsubstituted arylene group having 6 to 22 ring carbon atoms; and Ar101 is a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms.
In the organic EL device according to this exemplary embodiment, it is preferred that R201 to R208 in the third compound represented by formula (2) each independently represent: a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms; or a group represented by —Si(R90)(R902)(R903).
In the organic EL device according to this exemplary embodiment, it is preferred that R201 to R208 in the third compound represented by formula (2) be hydrogen atoms.
In the third compound, it is preferred that all groups described as “substituted or unsubstituted” be “unsubstituted” groups.
The third compound can be produced by methods known in the related art. Alternatively, the third compound can be produced based on a method known in the related art by selecting known alternative reaction(s) and materials according to the final product.
Specific examples of third compounds include, for instance, the following compounds, although the invention is not limited to these specific examples of third compounds. If the third compound is a compound represented by formula (1), specific examples of third compounds also include the compounds listed as specific examples of first compounds.
If the emitting layer of the organic EL device according to this exemplary embodiment contains second and third compounds, it is preferred that the relationship between the singlet energy S1(H3) of the third compound and that Si (D2) of the second compound(s) be as in the numerical formula below (Numerical Formula 1).
S
1(H3)>S1(D2) (Numerical Formula 1)
The following is an example of how to measure the singlet energy Si using a solution (also referred to as the solution method).
A toluene solution of a measurement target compound at a concentration ranging from 10−5 mol/L to 10−4 mol/L is prepared and put in a quartz cell. An absorption spectrum (ordinate axis: absorption intensity, abscissa axis: wavelength) of the thus-obtained sample is measured at a normal temperature (300K). A tangent is drawn to the fall of the absorption spectrum close to the long-wavelength region, and a wavelength value kedge (nm) at an intersection of the tangent and the abscissa axis is assigned to a conversion equation (F2) below to calculate singlet energy.
Conversion equation (F2): S1 [eV]=1239.85/λedge
An example of a system used to measure the absorption spectrum is Hitachi's spectrophotometer (model: U3310), although this is not the only system that can be used.
The tangent to the fall of the absorption spectrum close to the long-wavelength region is drawn as follows. While moving on a curve of the absorption spectrum from the local maximum value closest to the long-wavelength region, among the local maximum values of the absorption spectrum, in a long-wavelength direction, a tangent at each point on the curve is checked. An inclination of the tangent is decreased and increased in a repeated manner as the curve falls (i.e., a value of the ordinate axis is decreased). A tangent drawn at a point where the inclination of the curve is the local minimum closest to the long-wavelength region (except when absorbance is 0.1 or less) is defined as the tangent to the fall of the absorption spectrum close to the long-wavelength region.
The local maximum absorbance of 0.2 or less is not counted as the above-mentioned local maximum absorbance closest to the long-wavelength region.
Preferably, the thickness of the emitting layer of the organic EL device according to this exemplary embodiment is in a range from 5 nm to 50 nm, more preferably in a range from 7 nm to 50 nm, even more preferably in a range from 10 nm to 50 nm. An emitting layer that is 5 nm or thicker is easy to form, and, with such an emitting layer, it is easy to adjust chromaticity. An emitting layer that is 50 nm or thinner helps prevent an increase in drive voltage.
If the emitting layer contains second and third compounds, it is preferred that the content ratios of the second and third compounds in the emitting layer be, for example, in the following ranges.
Preferably, the content ratio of the third compound is in a range from 80% by mass to 99% by mass, more preferably in a range from 90% by mass to 99% by mass, even more preferably in a range from 95% by mass to 99% by mass.
Preferably, the content ratio of the second compound(s) is in a range from 1% by mass to 10% by mass, more preferably in a range from 1% by mass to 7% by mass, even more preferably in a range from 1% by mass to 5% by mass.
The upper limit to the total content ratio of the second and third compounds in the emitting layer, however, is 100% by mass.
It should be noted that this exemplary embodiment does not exclude the possibility that the emitting layer contains any material other than second and third compounds.
The emitting layer may contain one type of second compound alone or may contain two or more types thereof. The emitting layer may contain one type of third compound alone or may contain two or more types thereof.
The following further describes the structure of the organic EL device. Codes may be omitted in the following description.
The substrate is used as a support for the organic EL device. For instance, glass, quartz, plastics and the like are usable for the substrate. A flexible substrate is also usable. The flexible substrate is a bendable substrate, which is exemplified by a plastic substrate. Examples of the material for the plastic substrate include polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, and polyethylene naphthalate. Moreover, an inorganic vapor deposition film is also usable.
Metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a large work function (specifically, 4.0 eV or more) is preferably used as the anode formed on the substrate. Specific examples of the material include ITO (Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide and zinc oxide, and graphene. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chrome (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides of a metal material (e.g., titanium nitride) are usable.
The material is typically formed into a film by a sputtering method. For instance, the indium oxide-zinc oxide can be formed into a film by the sputtering method using a target in which zinc oxide in a range from 1 mass % to 10 mass % is added to indium oxide. Moreover, for instance, the indium oxide containing tungsten oxide and zinc oxide can be formed by the sputtering method using a target in which tungsten oxide in a range from 0.5 mass % to 5 mass % and zinc oxide in a range from 0.1 mass % to 1 mass % are added to indium oxide. In addition, the anode may be formed by a vacuum deposition method, a coating method, an inkjet method, a spin coating method or the like.
Among the organic layers formed on the anode, since the hole injecting layer adjacent to the anode is formed of a composite material into which holes are easily injectable irrespective of the work function of the anode, a material usable as an electrode material (e.g., metal, an alloy, an electroconductive compound, a mixture thereof, and the elements belonging to the group 1 or 2 of the periodic table) is also usable for the anode.
A material having a small work function such as elements belonging to Groups 1 and 2 in the periodic table of the elements, specifically, an alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys (e.g., MgAg and AlLi) including the alkali metal or the alkaline earth metal, a rare earth metal such as europium (Eu) and ytterbium (Yb), alloys including the rare earth metal are also usable for the anode. It should be noted that the vacuum deposition method and the sputtering method are usable for forming the anode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the anode, the coating method and the inkjet method are usable.
It is preferable to use metal, an alloy, an electroconductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less) for the cathode. Examples of the material for the cathode include elements belonging to Groups 1 and 2 in the periodic table of the elements, specifically, the alkali metal such as lithium (Li) and cesium (Cs), the alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), alloys (e.g., MgAg and AlLi) including the alkali metal or the alkaline earth metal, the rare earth metal such as europium (Eu) and ytterbium (Yb), and alloys including the rare earth metal.
It should be noted that the vacuum deposition method and the sputtering method are usable for forming the cathode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the cathode, the coating method and the inkjet method are usable.
By providing the electron injecting layer, various conductive materials such as Al, Ag, ITO, graphene, and indium oxide-tin oxide containing silicon or silicon oxide may be used for forming the cathode regardless of the work function. The conductive materials can be formed into a film using the sputtering method, inkjet method, spin coating method and the like.
The hole injecting layer is a layer containing a substance exhibiting a high hole injectability. Examples of the substance exhibiting a high hole injectability include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chrome oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, and manganese oxide.
In addition, the examples of the highly hole-injectable substance further include: an aromatic amine compound, which is a low-molecule organic compound, such that 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), 4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), and 3-[N-(1-naphthyl)-N-(9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1); and dipyrazino[2,3-f:20,30-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
In addition, a high polymer compound (e.g., oligomer, dendrimer and polymer) is usable as the substance exhibiting a high hole injectability. Examples of the high-molecule compound include poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), and poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD). Moreover, an acid-added high polymer compound such as poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) and polyaniline/poly(styrene sulfonic acid)(PAni/PSS) are also usable.
The organic EL device according to this exemplary embodiment may further include a hole transporting layer besides the first hole transporting layer.
An organic EL device according to an exemplary embodiment further includes a second hole transporting layer between the anode and the first hole transporting layer.
The organic EL device 1A includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10A between the anode 3 and the cathode 4. The organic layer 10A is formed by a hole injecting layer 6, a second hole transporting layer 72, a first hole transporting layer 71, an emitting layer 5, an electron transporting layer 8, and an electron injecting layer 9 stacked in this order on the anode 3.
The organic EL device 1C includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10A between the anode 3 and the cathode 4. The organic layer 10A is formed by a hole injecting layer 6, a second hole transporting layer 72, a first hole transporting layer 71, an emitting layer 5, an electron transporting layer 8, and an electron injecting layer 9 stacked in this order from on anode 3, and the emitting layer 5 includes a first emitting layer 51 and a second emitting layer 52.
If the organic EL device has a second hole transporting layer, the first hole transporting layer has a first surface close to the cathode and a second surface close to the anode, of the first hole transporting layer. The first surface of the first hole transporting layer is in direct contact with the emitting layer.
Preferably, the second hole transporting layer is directly adjacent to the first hole transporting layer. That is, it is preferred that the second surface of the first hole transporting layer be in direct contact with the second hole transporting layer.
Preferably, the second hole transporting layer contains a compound having an amino group. The compound having an amino group is, for example, an N-(LAMN1-LAMN2-LAMN3-ArAMN)3. The multiple LAMN1s, LAMN2S, LAMN3S, and ArAMNS may be the same as or different from each other. LAMN1, LAMN2, and LAMN3 are each a single bond, substituted or unsubstituted arylene group, or substituted or unsubstituted divalent heterocyclic group. ArAMN is a substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group. LAMN1, LAMN2, LAMN3, and ArAMN contain, for example, no pyrene structure.
It is also preferred that the second hole transporting layer contain a compound having only one amino group in its molecule (also referred to as a monoamine compound).
It is also preferred that the second hole transporting layer contain a compound represented by formula (B1) below.
In formula (B1),
LA1, LB1, and LC1 each independently represent: a single bond; a substituted or unsubstituted arylene group having 6 to 18 ring carbon atoms; or a substituted or unsubstituted divalent heterocyclic group having 5 to 13 ring atoms;
if LA1 and LB1 are single bonds, A1 and B1 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
if LA1 and LC1 are single bonds, A1 and C1 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
if LB1 and LC1 are single bonds, B1 and C1 are: bonded together to form a substituted or unsubstituted monocyclic ring; bonded together to form a substituted or unsubstituted fused ring; or not bonded together;
A1, B1, and C1 not forming the substituted or unsubstituted monocyclic ring and not forming the substituted or unsubstituted fused ring each independently represent: a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms; a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms; or a group represented by —Si(R921)(R922)(R923);
R921, R922, and R923 each independently represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms;
when multiple R921s are present, the multiple R921s are mutually the same or different;
when multiple R922s are present, the multiple R922s are mutually the same or different; and
when multiple R923s are present, the multiple R923s are mutually the same or different.
Preferably, the second hole transporting layer consists of a compound containing no pyrene structure.
It is also preferred that the second hole transporting layer consists of a compound having an amino group.
It is also preferred that the second hole transporting layer contain a compound having a carbazolyl group. The compound having a carbazolyl group is, for example, a Cz-(Lcz1-Lcz2-Lcz3-Arcz)1, Cz-(Lcz1-Lcz2-Lcz3-Arcz)2, or Cz-(Lcz1-Lcz2-Lcz3-Arcz)3. Cz is a carbazolyl group. Multiple Lcz1s, Lcz2s, Lcz3s, and Arczs may be the same as or different from each other. Lcz1 is bonded to a carbon atom or the nitrogen atom of Cz. Lcz1, Lcz2, and Lcz3 are each a single bond, substituted or unsubstituted arylene group, or substituted or unsubstituted divalent heterocyclic group. Arcz is a substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group. Lcz1, Lcz2, Lcz3, and Arcz contain, for example, no pyrene structure.
Any hole transporting layer other than the first hole transporting layer is a layer that contains a highly hole transporting substance. An aromatic amine compound, carbazole derivative, anthracene derivative and the like are usable for the hole transporting layer. Specific examples of a material for the hole transporting layer include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4-phenyl-4′-(9-phenylfluorene-9-yl)triphenylamine (abbreviation: BAFLP), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB). The above-described substances mostly have a hole mobility of 10−6 cm2/(V·s) or more.
For the hole transporting layer, a carbazole derivative such as CBP, 9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (CzPA), and 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (PCzPA) and an anthracene derivative such as t-BuDNA, DNA, and DPAnth may be used. A high polymer compound such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA) is also usable.
Preferably, the first and second hole transporting layers do not contain antimony chloride, vanadium oxide, molybdenum oxide, ruthenium oxide, tungsten oxide, zinc oxide, tin oxide, and iron oxide, more preferably do not contain inorganic compounds.
Preferably, the first and second hole transporting layers do not contain hexacyanoazatriphenylene.
However, in addition to the above substances, any substance exhibiting a higher hole transportability than an electron transportability may be used. It should be noted that the layer containing the substance exhibiting a high hole transportability may be not only a single layer but also a laminate of two or more layers formed of the above substance(s).
The organic EL device according to this exemplary embodiment may further has a third hole transporting layer as a hole transporting layer. Preferably, the third hole transporting layer is in direct contact with the side of the second hole transporting layer close to the anode.
The electron transporting layer is a layer containing a highly electron-transporting substance. For the electron transporting layer, 1) a metal complex such as an aluminum complex, beryllium complex, and zinc complex, 2) a heteroaromatic compound such as imidazole derivative, benzimidazole derivative, azine derivative, carbazole derivative, and phenanthroline derivative, and 3) a high polymer compound are usable. Specifically, as a low-molecule organic compound, a metal complex such as Alq, tris(4-methyl-8-quinolinato)aluminum (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium (abbreviation: BeBq2), BAlq, Znq, ZnPBO and ZnBTZ is usable. In addition to the metal complex, a heteroaromatic compound such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(ptert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), and 4,4′-bis(5-methylbenzoxazole-2-yl)stilbene (abbreviation: BzOs) is usable. In the exemplary embodiment, a benzimidazole compound is preferably usable. The above-described substances mostly have an electron mobility of 10−6 cm2/(V·s) or more. It should be noted that any substance other than the above substance may be used for the electron transporting layer as long as the substance exhibits a higher electron transportability than the hole transportability. The electron transporting layer may be provided in the form of a single layer or a laminate of two or more layers of the above substance(s).
Further, a high polymer compound is usable for the electron transporting layer. For instance, poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation: PF-Py), poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)](abbreviation: PF-BPy) and the like are usable.
The electron injecting layer is a layer containing a highly electron-injectable substance. Examples of a material for the electron injecting layer include an alkali metal, alkaline earth metal and a compound thereof, examples of which include lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), and lithium oxide (LiOx). In addition, the alkali metal, alkaline earth metal or the compound thereof may be added to the substance exhibiting the electron transportability in use. Specifically, for instance, magnesium (Mg) added to Alq may be used. In this case, the electrons can be more efficiently injected from the cathode.
Alternatively, the electron injecting layer may be provided by a composite material in a form of a mixture of the organic compound and the electron donor. Such a composite material exhibits excellent electron injectability and electron transportability since electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material excellent in transporting the generated electrons. Specifically, the above examples (e.g., the metal complex and the heteroaromatic compound) of the substance forming the electron transporting layer are usable. As the electron donor, any substance exhibiting electron donating property to the organic compound is usable. Specifically, the electron donor is preferably alkali metal, alkaline earth metal and rare earth metal such as lithium, cesium, magnesium, calcium, erbium and ytterbium. The electron donor is also preferably alkali metal oxide and alkaline earth metal oxide such as lithium oxide, calcium oxide, and barium oxide. Moreover, a Lewis base such as magnesium oxide is usable. Further, the organic compound such as tetrathiafulvalene (abbreviation: TTF) is usable.
A method for forming each layer of the organic EL device in the exemplary embodiment is subject to no limitation except for the above particular description. However, known methods of dry film-forming such as vacuum deposition, sputtering, plasma or ion plating and wet film-forming such as spin coating, dipping, flow coating or ink-jet are applicable.
A film thickness of each of the organic layers of the organic EL device in the exemplary embodiment is not limited unless otherwise specified in the above. In general, the thickness preferably ranges from several nanometers to 1 μm because excessively small film thickness is likely to cause defects (e.g. pin holes) and excessively large thickness leads to the necessity of applying high voltage and consequent reduction in efficiency.
According to this exemplary embodiment, an organic electroluminescence device with reduced drive voltage can be provided.
The organic EL device according to this exemplary embodiment has a first hole transporting layer containing a first compound, for example represented by formula (1), in direct contact with its emitting layer. Stacking the first hole transporting layer and the emitting layer in such a way improves the injection of holes into the emitting layer. The drive voltage, therefore, is reduced compared with that of known organic EL devices having a hole transporting layer made with a compound having an amino group.
An electronic device according to a second exemplary embodiment is installed with any one of the organic EL devices according to the above exemplary embodiment. Examples of the electronic device include a display device and a light-emitting device. Examples of the display device include a display component (e.g., an organic EL panel module), TV, mobile phone, tablet and personal computer. Examples of the light-emitting device include an illuminator and a vehicle light.
The scope of the invention is not limited to the above-described exemplary embodiments but includes any modification and improvement as long as such modification and improvement are compatible with the invention.
For instance, the emitting layer is not limited to a single layer, but may be provided by laminating two or more emitting layers. When the organic EL device has two or more emitting layers, it is only required that at least one of the emitting layers satisfies the conditions described in the above exemplary embodiments. For instance, the rest of the emitting layers may be a fluorescent emitting layer or a phosphorescent emitting layer with use of emission caused by electron transfer from the triplet excited state directly to the ground state.
When the organic EL device includes a plurality of emitting layers, these emitting layers may be mutually adjacently provided, or may form a so-called tandem organic EL device in which a plurality of emitting units are layered via an intermediate layer.
For instance, a blocking layer is optionally provided adjacent to the emitting layer close to the cathode. Preferably, the blocking layer provided on the side of the emitting layer close to the cathode is in direct contact with the emitting layer. Preferably, the blocking layer on the side of the emitting layer close to the cathode blocks at least one of holes or excitons.
For instance, when the blocking layer is provided in contact with the side of the emitting layer close to the cathode, the blocking layer permits transport of electrons, and blocks holes from reaching a layer provided closer to the cathode (e.g., the electron transporting layer) beyond the blocking layer. When the organic EL device includes the electron transporting layer, the blocking layer is preferably disposed between the emitting layer and the electron transporting layer.
Alternatively, the blocking layer may be provided adjacent to the emitting layer so that excitation energy does not leak out from the emitting layer toward neighboring layer(s). The blocking layer blocks excitons generated in the emitting layer from being transferred to a layer(s) (e.g., the electron transporting layer and the hole transporting layer) closer to the electrode(s) beyond the blocking layer.
The emitting layer is preferably bonded with the blocking layer.
Specific structure, shape and the like of the components in the invention may be designed in any manner as long as an object of the invention can be achieved.
The following describes the invention in further detail by providing examples. The invention is by no means limited to these examples.
The structures of the compounds represented by formula (1) used in the production of the organic EL devices according to Examples 1 to 17 are presented below.
The structures of the other compounds used in the production of the organic EL devices according to Examples 1 to 17 and Comparative Examples 1 to 22 are presented below.
Organic EL devices were fabricated as follows and tested.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 5-nm thick hole injecting layer was formed by depositing compound HA1 on the surface on the transparent electrode line side to cover the transparent electrode.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT1.
Following the formation of the third hole transporting layer, a 10-nm thick second hole transporting layer was formed by depositing compound HT2.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY1.
A 25-nm thick emitting layer was formed by co-depositing compound BH1 (host material (BH)) and compound BD1 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD1 would be 2% by mass.
A 10-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET1 on the emitting layer.
A 15-nm thick second electron transporting layer (ET) was formed by depositing compound ET2 on the first electron transporting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 1 is as follows.
ITO (130)/HA1 (5)/HT1 (80)/HT2 (10)/PY1 (5)/BH1:BD1 (25, 98%:2%)/ET1 (10)/ET2 (15)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, the percentages in parentheses (98%:2%) indicate the proportions of the host material (compound BH1) and compound BD1 in the emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 1 was fabricated in the same way as in Example 1, except that the thickness of the second hole transporting layer was changed to that in Table 1 and that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT3 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of the compound HT3 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT3.
Following the formation of the third hole transporting layer, a 10-nm thick second hole transporting layer was formed by depositing compound HT4.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY1.
A 20-nm thick emitting layer was formed by co-depositing compound BH2 (host material (BH)) and compound BD2 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD2 would be 4% by mass.
A 10-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET1 on the emitting layer.
A 15-nm thick second electron transporting layer (ET) was formed by depositing compound ET2 on the first electron transporting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 2 is as follows.
ITO (130)/HT3:HA2 (10, 97%:3%)/HT3 (80)/HT4 (10)/PY1 (5)/BH2:BD2 (20, 96%:4%)/ET1 (10)/ET2 (15)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT3 and HA2 in the hole injecting layer (% by mass), and another (96%:4%) indicates the proportions of the host material (compound BH2) and compound BD2 in the emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 2 was fabricated in the same way as in Example 2, except that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer and that the thickness of the emitting layer was changed to that in Table 2.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT3 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of compound HT3 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT3.
Following the formation of the third hole transporting layer, a 10-nm thick second hole transporting layer was formed by depositing compound HT4.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY1.
A 20-nm thick emitting layer was formed by co-depositing compound BH2 (host material (BH)) and compound BD2 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD2 would be 4% by mass.
A 10-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET3 on the emitting layer.
A 15-nm thick second electron transporting layer (ET) was formed by depositing compound ET2 on the first electron transporting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 3 is as follows.
ITO (130)/HT3:HA2 (10, 97%:3%)/HT3 (80)/HT4 (10)/PY1 (5)/BH2:BD2 (20, 96%:4%)/ET3 (10)/ET2 (15)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT3 and HA2 in the hole injecting layer (% by mass), and another (96%:4%) indicates the proportions of the host material (compound BH2) and compound BD2 in the emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 3 was fabricated in the same way as in Example 3, except that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer, and that the thickness of the emitting layer was changed to that in Table 3.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT3 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of compound HT3 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT3.
Following the formation of the third hole transporting layer, a 10-nm thick second hole transporting layer was formed by depositing compound HT5.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY1.
A 20-nm thick emitting layer was formed by co-depositing compound BH2 (host material (BH)) and compound BD2 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD2 would be 4% by mass.
A 10-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET1 on the emitting layer.
A 15-nm thick second electron transporting layer (ET) was formed by depositing compound ET2 on the first electron transporting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 4 is as follows.
ITO (130)/HT3:HA2 (10, 97%:3%)/HT3 (80)/HT5 (10)/PY1 (5)/BH2:BD2 (20, 96%:4%)/ET1 (10)/ET2 (15)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT3 and HA2 in the hole injecting layer (% by mass), and another (96%:4%) indicates the proportions of the host material (compound BH2) and compound BD2 in the emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 4 was fabricated in the same way as in Example 4, except that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer, and that the thickness of the emitting layer was changed to that in Table 4.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT3 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of compound HT3 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT3.
Following the formation of the third hole transporting layer, a 10-nm thick second hole transporting layer was formed by depositing compound HT5.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY1.
A 20-nm thick emitting layer was formed by co-depositing compound BH2 (host material (BH)) and compound BD2 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD2 would be 4% by mass.
A 10-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET3 on the emitting layer.
A 15-nm thick second electron transporting layer (ET) was formed by depositing compound ET2 on the first electron transporting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 5 is as follows.
ITO (130)/HT3:HA2 (10, 97%:3%)/HT3 (80)/HT5 (10)/PY1 (5)/BH2:BD2 (20, 96%:4%)/ET3 (10)/ET2 (15)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT3 and HA2 in the hole injecting layer (% by mass), and another (96%:4%) indicates the proportions of the host material (compound BH2) and compound BD2 in the emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 5 was fabricated in the same way as in Example 5, except that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer and that the thickness of the emitting layer was changed to that in Table 5.
The organic EL device of Comparative Example 6 was fabricated in the same way as in Example 1, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 1 following the formation of the hole injecting layer.
The organic EL device of Comparative Example 7 was fabricated in the same way as in Example 2, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 2 following the formation of the hole injecting layer.
The organic EL device of Comparative Example 8 was fabricated in the same way as in Example 3, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 3 following the formation of the hole injecting layer.
The organic EL devices fabricated in Examples 1 to 17 and Comparative Examples 1 to 22 were tested as follows. The test results are presented in Tables 1 to 13.
A voltage was applied across the cathode and the anode to a current density of 10 mA/cm2 and measured (unit: V).
As shown in Tables 1 to 5, the organic EL devices according to Examples 1 to 5 had a first hole transporting layer containing a first compound represented by formula (1) in direct contact with the emitting layer. Their drive voltage was lower than that of the devices according to Comparative Examples 1 to 5, which had a second hole transporting layer containing a material having an amine skeleton in direct contact with the emitting layer. As well as having a first hole transporting layer containing a first compound represented by formula (1) in direct contact with the emitting layer, furthermore, the organic EL devices according to Examples 1 to 5 had a second hole transporting layer containing a compound having an amino group in direct contact with the first hole transporting layer. Their drive voltage was lower than that of the devices according to Comparative Examples 6 to 8, which had the hole injecting layer in direct contact with the first hole transporting layer.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT6 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of the compound HT6 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 85-nm thick third hole transporting layer was formed by depositing compound HT6.
Following the formation of the third hole transporting layer, a 2.5-nm thick second hole transporting layer was formed by depositing compound HT7.
Following the formation of the second hole transporting layer, a 2.5-nm first hole transporting layer was formed by depositing compound PY2.
A 20-nm thick emitting layer was formed by co-depositing compound BH3 (host material (BH)) and compound BD3 (dopant material (BD)) on the first hole transporting layer in such a manner that the proportion of compound BD3 would be 2% by mass.
A 5-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET4 on the emitting layer.
A 25-nm thick second electron transporting layer (ET) was formed by co-depositing compound ET5 and the compound Liq on the first electron transporting layer (HBL). In this second electron transporting layer (ET), the proportion of compound ET5 was 50% by mass, and that of the compound Liq was 50% by mass. Liq is short for (8-quinolinolato)lithium.
A 1-nm thick electron injecting layer was formed by depositing Liq on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 6 is as follows.
ITO (130)/HT6:HA2 (10, 97%:3%)/HT6 (85)/HT7 (2.5)/PY2 (2.5)/BH3:BD3 (20, 98%:2%)/ET4 (5)/ET5:Liq (25, 50%:50%)/Liq (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT6 and HA2 in the hole injecting layer (% by mass), another (98%:2%) indicates the proportions of the host material (compound BH3) and compound BD3 in the emitting layer (% by mass), and another (50%:50%) indicates the proportions of compound ET5 and Liq in the second electron transporting layer (ET) (% by mass). The same applies hereinafter.
The organic EL device of Comparative Example 9 was fabricated in the same way as in Example 6, except that the thickness of the second hole transporting layer was changed to that in Table 6, and that the emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
The organic EL device of Comparative Example 10 was fabricated in the same way as in Example 6, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 6 following the formation of the hole injecting layer.
The organic EL device of Example 7 was fabricated in the same way as in Example 6, except that in the formation of the first hole transporting layer, the compound for the first hole transporting layer was changed to that in Table 7.
The organic EL device of Comparative Example 11 was fabricated in the same way as in Comparative Example 10, except that in the formation of the first hole transporting layer, compound PY2, for the first hole transporting layer, was changed to PY3 as in Table 7.
The organic EL device of Example 8 was fabricated in the same way as in Example 6, except that in the formation of the first hole transporting layer, compound PY2, for the first hole transporting layer, was changed to compound PY4 as in Table 8 and that in the formation of the emitting layer, furthermore, compound BH3, for the emitting layer, was changed to compound BH4 as in Table 8.
The organic EL device of Comparative Example 12 was fabricated in the same way as in Comparative Example 9, except that in the formation of the emitting layer, compound BH3, for the emitting layer, was changed to compound BH4 as in Table 8.
The organic EL device of Comparative Example 13 was fabricated in the same way as in Comparative Example 10, except that in the formation of the first hole transporting layer, compound PY2, for the first hole transporting layer, was changed to compound PY4 as in Table 8 and that in the formation of the emitting layer, furthermore, compound BH3, for the emitting layer, was changed to compound BH4 as in Table 8.
The organic EL device of Example 9 was fabricated in the same way as in Example 8, except that in the formation of the first hole transporting layer, compound PY4, for the first hole transporting layer, was changed to compound PY5 as in Table 9.
The organic EL device of Comparative Example 14 was fabricated in the same way as in Comparative Example 13, except that in the formation of the first hole transporting layer, compound PY4, for the first hole transporting layer, was changed to compound PY5 as in Table 9.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT6 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of the compound HT6 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT6.
Following the formation of the third hole transporting layer, a 2.5-nm thick second hole transporting layer was formed by depositing compound HT7.
Following the formation of the second hole transporting layer, a 2.5-nm first hole transporting layer was formed by depositing compound PY2.
A 12.5-nm thick first emitting layer was formed by co-depositing compound PY2 (host material) and compound BD3 (dopant material) on the first hole transporting layer in such a manner that the proportion of compound BD3 would be 2% by mass.
A 12.5-nm thick second emitting layer was formed by co-depositing compound BH3 (host material) and compound BD3 (dopant material) on the first emitting layer in such a manner that the proportion of compound BD3 would be 2% by mass.
A 5-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET4 on the second emitting layer.
A 25-nm thick second electron transporting layer (ET) was formed by co-depositing compound ET5 and the compound Liq on the first electron transporting layer (HBL). In this second electron transporting layer (ET), the proportion of compound ET5 was 50% by mass, and that of the compound Liq was 50% by mass.
A 1-nm thick electron injecting layer was formed by depositing Liq on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 10 is as follows.
ITO (130)/HT6:HA2 (10, 97%:3%)/HT6 (80)/HT7 (2.5)/PY2 (2.5)/PY2:BD3 (12.5, 98%:2%)/BH3:BD3 (12.5, 98%:2%)/ET4 (5)/ET5:Liq (25, 50%:50%)/Liq (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT6 and HA2 in the hole injecting layer (% by mass), other two (98%:2%) indicate the proportions of the host material (compound PY2 or BH3) and compound BD3 in the emitting layers (% by mass), and another (50%:50%) indicates the proportions of compound ET5 and Liq in the second electron transporting layer (ET) (% by mass). The same applies hereinafter.
The organic EL device of Example 11 was fabricated in the same way as in Example 10, except that the thickness of the second hole transporting layer and that of the first hole transporting layer were changed to those in Table 10.
The organic EL device of Comparative Example 15 was fabricated in the same way as in Example 10, except that the thickness of the second hole transporting layer was changed to that in Table 10 and that the first emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
The organic EL device of Comparative Example 16 was fabricated in the same way as in Example 10, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 10 following the formation of the hole injecting layer.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 10-nm thick hole injecting layer was formed by co-depositing compounds HT6 and HA2 on the surface on the transparent electrode line side to cover the transparent electrode. In this hole injecting layer, the proportion of the compound HT6 was 97% by mass, and that of compound HA2 was 3% by mass.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT6.
Following the formation of the third hole transporting layer, a 4-nm thick second hole transporting layer was formed by depositing compound HT7.
Following the formation of the second hole transporting layer, a 1-nm first hole transporting layer was formed by depositing compound PY3.
A 10-nm thick first emitting layer was formed by co-depositing compound PY4 (host material) and compound BD3 (dopant material) on the first hole transporting layer in such a manner that the proportion of compound BD3 would be 2% by mass.
A 15-nm thick second emitting layer was formed by co-depositing compound BH4 (host material) and compound BD3 (dopant material) on the first emitting layer in such a manner that the proportion of compound BD3 would be 2% by mass.
A 5-nm thick first electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET4 on the second emitting layer.
A 25-nm thick second electron transporting layer (ET) was formed by co-depositing compound ET5 and the compound Liq on the first electron transporting layer (HBL). In this second electron transporting layer (ET), the proportion of compound ET5 was 50% by mass, and that of the compound Liq was 50% by mass.
A 1-nm thick electron injecting layer was formed by depositing Liq on the second electron transporting layer.
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 12 is as follows.
ITO (130)/HT6:HA2 (10, 97%:3%)/HT6 (80)/HT7 (4)/PY3 (1)/PY4:BD3 (10, 98%:2%)/BH4:BD3 (15, 98%:2%)/ET4 (5)/ET5:Liq (25, 50%:50%)/Liq (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (97%:3%) indicate the proportions of compounds HT6 and HA2 in the hole injecting layer (% by mass), other two (98%:2%) indicate the proportions of the host material (compound PY4 or BH4) and compound BD3 in the emitting layers (% by mass), and another (50%:50%) indicates the proportions of compound ET5 and Liq in the second electron transporting layer (ET) (% by mass). The same applies hereinafter.
The organic EL device of Example 13 was fabricated in the same way as in Example 12, except that the thickness of the second hole transporting layer, that of the first hole transporting layer, and that of the first emitting layer were changed to those in Table 11.
The organic EL device of Comparative Example 17 was fabricated in the same way as in Example 12, except that the thickness of the second hole transporting layer was changed to that in Table 11 and that the first emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
The organic EL device of Comparative Example 18 was fabricated in the same way as in Example 12, except for the following. As in Table 11, instead of forming the third hole transporting layer, an 80-nm second hole transporting layer was formed by depositing compound PY2 following the formation of the hole injecting layer. Following the formation of the second hole transporting layer, a 5-nm thick first hole transporting layer was formed by depositing compound PY3.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 5-nm thick hole injecting layer was formed by depositing compound HA3 on the surface on the transparent electrode line side to cover the transparent electrode.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT8.
Following the formation of the third hole transporting layer, a 7.5-nm thick second hole transporting layer was formed by depositing compound HT9.
Following the formation of the second hole transporting layer, a 2.5-nm first hole transporting layer was formed by depositing compound PY6.
A 7.5-nm thick first emitting layer was formed by co-depositing compound PY6 (host material) and compound BD1 (dopant material) on the first hole transporting layer in such a manner that the proportion of compound BD1 would be 2% by mass.
A 17.5-nm thick second emitting layer was formed by co-depositing compound BH1 (host material) and compound BD1 (dopant material) on the first emitting layer in such a manner that the proportion of compound BD1 would be 2% by mass.
A 10-nm thick electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET3 on the second emitting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the electron transporting layer (HBL).
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 14 is as follows.
ITO (130)/HA3 (5)/HT8 (80)/HT9 (7.5)/PY6 (2.5)/PY6:BD1 (7.5, 98%:2%)/BH1:BD1 (17.5, 98%:2%)/ET3 (10)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, the set of percentages in parentheses (98%:2%) indicates the proportions of the host material (compound PY6 or BH1) and compound BD1 in the first or second emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Example 15 was fabricated in the same way as in Example 14, except that in the formation of the second and first hole transporting layers, the thickness of the second hole transporting layer and that of the first hole transporting layer were changed to those in Table 12.
The organic EL device of Comparative Example 19 was fabricated in the same way as in Example 14, except that the thickness of the second hole transporting layer was changed to that in Table 12 and that the first emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
The organic EL device of Comparative Example 20 was fabricated in the same way as in Example 14, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 12 following the formation of the hole injecting layer.
A 25 mm×75 mm×1.1 mm thick glass substrate with an ITO (Indium Tin Oxide) transparent electrode (anode) (Geomatec Co., Ltd.) was ultrasonic-cleaned in isopropyl alcohol for 5 minutes and then cleaned with UV ozone for 30 minutes. The thickness of the ITO transparent electrode was 130 nm.
The cleaned glass substrate with a transparent electrode line was attached to the substrate holder of a vacuum deposition system. Then, first, a 5-nm thick hole injecting layer was formed by depositing compound HA3 on the surface on the transparent electrode line side to cover the transparent electrode.
Following the formation of the hole injecting layer, an 80-nm thick third hole transporting layer was formed by depositing compound HT8.
Following the formation of the third hole transporting layer, a 5-nm thick second hole transporting layer was formed by depositing compound HT9.
Following the formation of the second hole transporting layer, a 5-nm first hole transporting layer was formed by depositing compound PY7.
A 12.5-nm thick first emitting layer was formed by co-depositing compound PY7 (host material) and compound BD1 (dopant material) on the first hole transporting layer in such a manner that the proportion of compound BD1 would be 2% by mass.
A 12.5-nm thick second emitting layer was formed by co-depositing compounds BH5 and BH6 (host materials) and compound BD1 (dopant material) on the first emitting layer. In the second emitting layer, the proportion of compound BH5 was 58.8% by mass, that of compound BH6 was 39.2% by mass, and that of compound BD1 was 2% by mass.
A 10-nm thick electron transporting layer (also referred to as the hole blocking layer) (HBL) was formed by depositing compound ET3 on the second emitting layer.
A 1-nm thick electron injecting layer was formed by depositing LiF on the electron transporting layer (HBL).
An 80-nm thick cathode was formed by depositing metal Al on the electron injecting layer.
A brief description of the device structure in Example 16 is as follows.
ITO (130)/HA3 (5)/HT8 (80)/HT9 (5)/PY7 (5)/PY7:BD1 (12.5, 98%:2%)/BH5:BH6:BD1 (12.5, 58.8%:39.2%:2%)/ET3 (10)/LiF (1)/Al (80)
The number in parentheses indicates the thickness of the layer (unit: nm).
Likewise, a set of percentages in parentheses (98%:2%) indicates the proportions of the host material (compound PY7) and compound BD1 in the first emitting layer (% by mass), and another (58.8%:39.2%:2%) indicates the proportions of compounds BH5, BH6, and BD1 in the second emitting layer (% by mass). The same applies hereinafter.
The organic EL device of Example 17 was fabricated in the same way as in Example 16, except that in the formation of the second and first hole transporting layers, the thickness of the second hole transporting layer and that of the first hole transporting layer were changed to those in Table 13.
The organic EL device of Comparative Example 21 was fabricated in the same way as in Example 16, except that the thickness of the second hole transporting layer was changed to that in Table 13 and that the first emitting layer was formed in direct contact with the second hole transporting layer instead of forming the first hole transporting layer.
The organic EL device of Comparative Example 22 was fabricated in the same way as in Example 16, except that instead of forming the third and second hole transporting layers, the first hole transporting layer was formed to the thickness in Table 13 following the formation of the hole injecting layer.
A toluene solution of compound BD1 was prepared by dissolving compound BD1 in toluene at a concentration of 4.9×10−6 mol/L.
Toluene solutions of compounds BD2 and BD3 were prepared in the same way as that of compound BD1.
Using a fluorescence spectrum analyzer (F-7000 spectrophotofluorometer (Hitachi High-Tech Science Corporation)), the toluene solutions of compounds BD1, BD2, and BD3 were excited at 390 nm, and the maximum fluorescence peak wavelength was measured.
The maximum fluorescence peak wavelength of compound BD1 was 453 nm.
The maximum fluorescence peak wavelength of compound BD2 was 450 nm.
The maximum fluorescence peak wavelength of compound BD3 was 455 nm.
1 . . . Organic EL device, 1A . . . organic EL device, 2 . . . substrate, 3 . . . anode, 4 . . . cathode, 5 . . . emitting layer, 6 . . . hole injecting layer, 71 . . . first hole transporting layer, 72 . . . second hole transporting layer, 8 . . . electron transporting layer, 9 . . . electron injecting layer, 10 . . . organic layer, 10A . . . organic layer.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-203199 | Nov 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/041599 | 11/6/2020 | WO |
