Patent Application
20210384430
The invention relates to an organic elecrtoluminescence device and an electronic apparatus provided with the organic electroluminescence device.
When a voltage is applied to an organic electroluminescence device (hereinafter may be referred to as an organic EL device), holes are injected to an emitting layer from an anode and electrons are injected to an emitting layer from a cathode. In the emitting layer, injected holes and electrons are re-combined and excitons are formed.
Patent Document 1 to 4 disclose anthracene compounds having a specific structure used as a host material for an emitting layer in an organic electroluminescence device.
As a material for an organic EL device, various materials we studied to decrease CIEy value in CIE1931 chromaticity diagram. However, a lifetime of an organic EL device becomes shorter when trying to decrease CIEy value, and thus, it is difficult to obtain an organic EL device which satisfies both the properties.
An object of the invention is to provide an organic EL device having a low CIEy value and a long lifetime, and to provide an electronic apparatus provided with the organic EL device.
As a result or extensive studies, the inventors have found that by using a compound represented by formula (1) (host material) and a compound having specific structure (one or more compounds selected from the group consisting of compounds represented by each of formulas (11), (21), (31), (41), (51), (61), (71) and (81): dopant material) in combination, an organic EL device having a low CIEy value and a long lifetime can be obtained, and they have achieved the invention.
According to the invention, the following organic EL device and electric apparatus can be provided.
a cathode,
an anode, and
an emitting layer disposed between the cathode and the anode, wherein
the emitting layer comprises a compound represented by the following formula (1) and one or more compounds selected from the group consisting of a compound represented by formula (11), a compound represented by formula (21), a compound represented by formula (31), a compound represented by formula (41), a compound represented by formula (51), a compound represented by formula (61), a compound represented by formula (71) and a compound represented by formula (81):
wherein in the formula (1),
R1 to R8 are independently
R901 to R907 are independently
when two or more of R901 to R907 exist, two or more of R901 to R907 may be the same with or different from each other,
at least one of R1 to R8 is a deuterium atom;
two or more adjacent groups of R1 to R4 do not form a ring by bonding with each other, and two or more adjacent groups of R5 to R8 do not form a ring by bonding with each other,
L1 and L2 are independently
Ar1 and Ar2 are independently
when L1, L2, Ar1 and Ar2 have a substituent, the substituent is
wherein, in the formula (11),
one or more pairs of two or more adjacent groups of R101 to R110 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
at least one of R101 to R110 is a monovalent group represented by the formula (12);
R101 to R110 that do not form the substituted or unsubstituted, saturated or unsaturated ring and that are not a monovalent group represented by the following formula (12) are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (12), Ar101 and Ar102 are independently
L101 to L103 are independently
Zs are independently CRa or N;
A1 ring and A2 ring are independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, or a substituted a unsubstituted heterocyclic ring having 5 to 50 ring atoms;
when a plurality of Ras exist, two or more adjacent groups of Ra are bonded with each other to form a substituted a unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
when a plurality of Rbs exist, one or more pairs of two or more adjacent groups of Rb are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
when a plurality of Rcs exist, one a more pars of two or more adjacent groups of Rc are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
n21 and n22 are independently an integer of 0 to 4;
Ra to Rc that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
wherein, in the formula (31),
one or more pairs of two or more adjacent groups of R301 to R307 and R311 to R317 form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring;
R301 to R307 and R311 to R317 that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R321 and R322 are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (41),
a ring, b ring and c ring are independently
R401 and R402 are independently bonded to the a ring, the b ring or the c ring to form a substituted or unsubstituted heterocyclic ring or do not form a substituted or unsubstituted heterocyclic ring;
R401 and R402 that do not form the substituted or unsubstituted heterocyclic ring are independently
wherein, in the formula (51),
r ring is a ring represented by the formula (52) or formula (53) which is fused to an adjacent ring at an arbitrary position;
q ring and s ring are independently a ring represented by the formula (54) which is fused to an adjacent ring at an arbitrary position;
p ring and t ring are independently a ring represented by the formula (55) or the formula (56) which is fused to an adjacent ring at an arbitrary position;
when a plurality of R501s exist, adjacent R501s are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
X501 is an oxygen atom, a sulfur atom, or NR502;
R501 and R502 that do not form the substituted or unsubstituted saturated or unsaturated ring are a hydrogen atom,
R901 to R907 are as defined in the formula (1);
Ar501 and Ar502 are independently
L501 is
m1 is an integer of 0 to 2, m2 is an integer of 0 to 4, m3s are independently an integer of 0 to 3, and m4s are independently an integer of 0 to 5, when a plurality of R501s exist, R501s may be the same or different;
wherein, in the formula (61),
at least one pair of R601 and R602, R602 and R603, and R603 and R604 are bonded with each other to form a divalent group represented by the formula (62),
at least one pair of R605 and R606, R606 and R607, and R607 and R608 are bonded with each other to form a divalent group represented by formula (63);
at least one of R601 to R604 that does not form the divalent group represented by the formula (62), and R611 to R614 is a monovalent group represented by the following formula (64);
at least one of R605 to R606 that do not form the divalent group represented by the formula (63), and R621 to R624 is a monovalent group represented by the following formula (64);
X601 is an oxygen atom, a sulfur atom, or NR609;
R601 to R608 that do not form the divalent group represented by the formulas (62) and (63) and that is not the monovalent group represented by the formula (64), R611 to R614 and R621 to R624 that are not the monovalent group represented by the formula (64), and R609 are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (64), Ar601 and Ar602 are independently
L601 to L603 are independently
wherein, in the formula (71),
A701 ring and A702 ring are independently
One or more rings selected from the group consisting of A701 ring and A702 ring are bonded to the bond * of the structure represented by the following formula (72);
wherein, in the formula (72),
A703 rings are independently
X701 is NR703, C(R704)(R705), Si(R706)(R707), Ge(R706)(R709), O, S or Se;
R701 and R702 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form a substituted or unsubstituted saturated or unsaturated ring;
R701 and R702 that do not form the substituted or unsubstituted, saturated or unsaturated ring, and R703 to R709 are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (81),
A801 ring is a ring represented by the formula (82) which is fused to an adjacent ring at an arbitrary position;
A802 ring is a ring represented by the formula (83) which is fused to an adjacent ring at an arbitrary position;
two bonds * bond to A803 ring at an arbitrary position;
X801 and X802 are independently C(R803)(R804), Si(R805)(R806), an oxygen atom, or a sulfur atom;
A803 ring is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms;
Ar801 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms;
R801 to R806 are independently
R901 to R907 are as defined in the formula (1);
m801 and m802 are independently an integer of 0 to 2; when m801 is 2, R801's may be the same as or different from each other, and when m802 is 2, R802's may be the same as or different from each other;
a801 is an integer of 0 to 2; when a801 is 0 or 1, the structure in the parentheses indicated by “3-a801” may be the same or different from each other; when a801 is 2, Ar801s may be the same or different from each other. 2. An electronic apparatus provided with the organic electroluminescence device according to the above 1.
According to the invention, an organic EL device having a low CIEy value and a long lifetime, and an electronic apparatus provided with the organic EL device can be provided.
In this specification, a hydrogen atom means an atom including isotopes different in the number of neutrons, namely, a protium, a deuterium and a tritium.
In the this specification, to a bondable position in which a symbol such as “R”, or “D” representing a deuterium atom is not specified in a chemical formula, a hydrogen atom, that is, a light hydrogen atom, a deuterium atom, or a tritium atom is bonded thereto.
In the this specification, a term “ring carbon atoms” represents the number of carbon atoms among atoms forming a subject ring itself of a compound having a structure in which atoms are bonded in a ring form (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound or a heterocyclic compound). When the subject ring is substituted by a substituent, the carbon contained in the substituent is not included in the number of ring carbon atoms. The same shall apply to the “ring carbon atoms” described below, unless otherwise noted. For example, 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 example, a 9,9-diphenylfluorenyl group has 13 ring carbon atoms, and a 9,9′-spirobifluorenyl group has 25 ring carbon atoms.
Further, when the benzene ring or the naphthalene ring is substituted by an alkyl group as a substituent, for example, the number of carbon atoms of the alkyl group is not included the ring carbon atoms.
In the this specification, a term “ring atoms” represents the number of atoms forming a subject ring itself of a compound having a structure in which atoms are bonded in a ring form (for example, a monocycle, a fused ring and a ring assembly) (for example, a monocyclic compound, a fused ring compound, a cross-linked compound, a carbocyclic compound or a heterocyclic compound). The term “ring atoms” does not include atoms which do not form the ring (for example, a hydrogen atom which terminates a bond of the atoms forming the ring) or atoms contained in a substituent when the ring is substituted by the substituent. The same shall apply to the “trig atoms” described below, unless otherwise noted. For example, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. A hydrogen atom bonded with a carbon atom of the pyridine ring or the quinazoline ring or an atom forming the substituent is not included in the number of the ring atoms.
In the this specification, a term “XX to YY carbon atoms” in an expression of “substituted or unsubstituted ZZ group inducing XX to YY carbon atoms” represents the number of carbon atoms when the ZZ group is unsubstituted. The number of carbon atoms of a substituent when the ZZ group is substituted is not included. Here, “YY” is larger than “XX”, and “XX” and “YY” each mean an integer of 1 or more.
In the this specification, a term “XX to YY atoms” in an expression of “substituted or unsubstituted ZZ group including XX to YY atoms” represents the number of atoms when the ZZ group is unsubstituted. The number of atoms of a substituent when the group is substituted is not included. Here, “YY” is larger than “XX”, and “XX” and “YY” each mean an integer of 1 or more.
A term “unsubstituted” in the case of “substituted or unsubstituted ZZ group” means that the ZZ group is not substituted by a substituent, and a hydrogen atom is bonded therewith. Alternatively, a term “substituted” in the case of “substituted or unsubstituted ZZ group” means that one or more hydrogen atoms in the ZZ group are substituted by a substituent. Similarly, a term “substituted” in the case of “BB group substituted by an AA group” means that one or more hydrogen atoms in the BB group are substituted by the AA group.
Hereinafter, the substituent deserted herein will be described.
The number of the ring carbon atoms of the “unsubstituted aryl group” described herein is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
The number of the ring carbon atoms of the “unsubstituted heterocyclic group” described herein is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise specified.
The number of the carbon atoms of the “unsubstituted alkyl group” described herein is 1 to 50, preferably 1 to 20, and more preferably 1 b 6, unless otherwise specified.
The number of the carbon atoms of the “unsubstituted alkenyl group” described herein is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise specified.
The number of the carbon atoms of the “unsubstituted alkynyl group” in is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise specified.
The number of the ring cotton atoms of the “unsubstituted cycloalkyl group”described herein is 3 to 50, preferably 3 to 20, and more preferably 3 to 6, unless otherwise specified.
The number of the ring carbon atoms of the “unsubstituted arylene group” described herein is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
The number of the ring atoms of the “unsubstituted divalent heterocyclic group” described herein is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise specified.
The number of the carbon atoms of the “unsubstituted alkylene group” described herein is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise specified.
Specific examples (specific example group G1) of “substituted or unsubstituted aryl group” described herein include an unsubstituted aryl group and a substituted aryl group described below. (Here, a term “unsubstituted aryl group” refers to a case where the “substituted or unsubstituted aryl group” is the “unsubstituted aryl group,” and a term “substituted aryl group” refers to a case where the “substituted or unsubstituted aryl group” is the “substituted aryl group”. Hereinafter, a case of merely “aryl group” hawks both the “unsubstituted aryl group” and the “substituted aryl group”.
The “substituted aryl group” refers to a case where the “unsubstituted aryl group” has a substituent, and specific examples thereof include a group in which the “unsubstituted aryl group” has the substituent, and a substituted aryl group described below. It should be noted that examples of the “unsubstituted aryl group” and examples of the “substituted aryl group” listed herein are only one example, and the “substituted aryl group” described herein also includes a group in which a group in which “unsubstituted aryl group” has a substituent further has a substituent, and a group in which “substituted aryl group” further has a substituent, and the like.
An unsubstituted aryl group:
A substituted aryl group:
The “heterocyclic group” described herein is a ring group at least one hetero atom in the ring atom. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom and a boron atom.
The “heterocyclic group” described herein may be a monocycle group, or a fused ring group.
The “heterocyclic group” described herein may be an aromatic heterocyclic group, or an aliphatic heterocyclic group.
Specific examples (specific example group G2) of the “substituted or unsubstituted heterocycle group” include an unsubstituted heterocyclic group and a substituted heterocycle group described below. (Here, the unsubstituted heterocyclic group refers to a case where the “substituted or unsubstituted heterocyclic group” is the “unsubstituted heterocyclic group,” and the substituted heterocyclic group refers to a case where the “substituted or unsubstituted heterocyclic group” is the “substituted heterocyclic group”. Hereinafter, the cased merely “heterocyclic group” includes both the “unsubstituted heterocyclic group” and the “substituted heterocyclic group”.
The “substituted heterocyclic group” refers to a case where the “unsubstituted heterocyclic group” has a substituent, and specific examples thereof include a group in which the “unsubstituted heterocyclic group” has a substituent, and a substituted heterocycle group described below. It should be noted that examples of the “unsubstituted heterocyclic group” and examples of the “substituted heterocyclic group” listed herein are merely one example, and the “substituted heterocyclic group” described herein also includes a group in which “unsubstituted heterocyclic group” which has a substituent further has a substituent, and a group in which “substituted heterocyclic group” further has a substituent, and the like.
An unsubstituted heterocyclic group including a nitrogen atom:
An unsubstituted heterocyclic group including an oxygen atom:
An unsubstituted heterocyclic group a sulfur atom:
A substituted heterocyclic group including a nitrogen atom:
A substituted heterocyclic group indicting an oxygen atom:
A substituted heterocyclic group including a sulfur atom:
A monovalent group derived from the following unsubstituted heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom by removal of one hydrogen atom bonded to the ring atoms thereof, and a monovalent group in which a monovalent group derived from the following unsubstituted heterocyclic ring has a substituent by removal of one hydrogen atom bonded to the ring atoms thereof:
In the formulas (XY-1) to (XY-18), XA and YA are independently an oxygen atom, a sulfur atom, NH or CH2. However, at least one of XA and YA is an oxygen atom, a sulfur atom or NH.
The heterocyclic ring represented by the formulas (XY-1) to (XY-18) becomes a monovalent heterocyclic group including a bond at an arbitrary position.
An expression “the monovalent group derived from the unsubstituted heterocyclic ring represented by the formulas (XY-1) to (XY-18) has a substituent” refers to a case where the hydrogen atom bonded with the carbon atom which constitutes a skeleton of the formulas is substituted by a substituent, or a state in which XA or YA is NH or CH2, and the hydrogen atom in the NH or CH2 is replaced with a substituent.
Specific examples (specific example group G3) of the “substituted or unsubstituted alkyl group” include an unsubstituted alkyl group and a substituted alkyl group described below. (Here, the unsubstituted alkyl group refers to a case where the “substituted or unsubstituted alkyl group” is the “unsubstituted alkyl group,” and the substituted alkyl group refers to a case where the “substituted or unsubstituted alkyl group” is the “substituted alkyl group”). Hereinafter, the case of merely “alkyl group” includes both the “unsubstituted alkyl group” and the “substituted alkyl group”.
The “substituted alkyl group” refers to a case where the “unsubstituted alkyl group” has a substituent, and specific examples thereof include a group in which the “unsubstituted alkyl group” has a substituent, and a substituted alkyl group described below. It should be noted that examples of the “unsubstituted alkyl group” and examples of the “substituted alkyl group” listed herein are merely one example, and the “substituted alkyl group” described herein also includes a group in which “unsubstituted alkyl group” has a substituent further has a substituent, a group in which “substituted alkyl group” further has a substituent, and the like.
An unsubstituted alkyl group:
A substituted alkyl group:
Specific examples (specific example group G4) of the “substituted or unsubstituted alkenyl group” include an unsubstituted alkenyl group and a substituted alkenyl group described below. (Here, the unsubstituted alkenyl group refers to a case where the “substituted or unsubstituted alkenyl group” is the “unsubstituted alkenyl group,” and the substituted alkenyl group refers to a case where the “substituted or unsubstituted alkenyl group” is the “substituted alkenyl group”). Hereinafter, the case of merely “alkenyl group” includes both the “unsubstituted alkenyl group” and the “substituted alkenyl group”.
The “substituted alkenyl group” refers to a case where the “unsubstituted alkenyl group” has a substituent, and specific examples thereof include a group in which the “unsubstituted alkenyl group” has a substituent, and a substituted alkenyl group described below. It should be noted that examples of the “unsubstituted alkenyl group” and examples of the “substituted alkenyl group” listed herein are merely one example, and the “substituted alkenyl group” described herein also includes a group in which “unsubstituted alkenyl group” has a substituent further has a substituent, a group in which “substituted alkenyl group” further has a substituent, and the like.
An unsubstituted alkenyl group and a substituted alkenyl group:
Specific examples (specific example group G5) of the “substituted or unsubstituted alkynyl group” include an unsubstituted alkynyl group described below. (Here, the unsubstituted alkynyl group refers to a case where the “substituted or unsubstituted alkynyl group” is the “unsubstituted alkynyl group”). Hereinafter, a case of merely “alkynyl group” includes both the “unsubstituted alkynyl group” and the “substituted alkynyl group”.
The “substituted alkynyl group” refers to a case where the “unsubstituted alkynyl group” has a substituent, and specific examples thereof include a group in which the “unsubstituted alkynyl group” described below has a substituent.
An unsubstituted alkynyl group:
Specific examples (specific example group G6) of the “substituted or unsubstituted cycloalkyl group” described herein include an unsubstituted cycloalkyl group and a substituted cycloalkyl group described below. (Here, the unsubstituted cycloalkyl group refers to a case where the “substituted or unsubstituted cycloalkyl group” is the “unsubstituted cycloalkyl group,” and the substituted cycloalkyl group refers to a case where the “substituted or unsubstituted cycloalkyl group” is the “substituted cycloalkyl group”). Hereinafter, a case of merely “cycloalkyl group” includes both the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group”.
The “substituted cycloalkyl group” refers to a case where the “unsubstituted cycloalkyl group” a the substituent, and specific examples thereof in include a group in which the “unsubstituted cycloalkyl group” has a substituent, and a substituted cycloalkyl group described below. It should be noted that examples of the “unsubstituted cycloalkyl group” and examples of the “substituted cycloalkyl group” listed herein are merely one example, and the “substituted cycloalkyl group” described herein also includes a group in which “unsubstituted cycloalkyl group” has a substituent further has a substituent, a group in which “substituted cycloalkyl group” further has a substituent, and the like.
An unsubstituted aliphatic ring group:
A substituted cycloalkyl group:
Specific examples (specific example group G7) cf the group represented by —Si(R901)(R902)(R903) described herein include
In which,
G1 is the “aryl group” described in the specific example group G1.
G2 is the “heterocyclic group” described in the specific example group G2.
G3 is the “alkyl group” described in the specific example group G3.
G5 is the “alkynyl group” described in the specific example group G5.
G6 is the “cycloalkyl group” described in the specific example group G6.
Specific examples (specific example group G8) of the group represented by —O—(R904) described herein include
In which,
G1 is the “aryl group” described in the specific example group G1.
G2 is the “heterocyclic group” described in the specific example group G2.
G3 is the “alkyl group” described in the specific example group G3.
G6 is the “cycloalkyl group” described in the specific example group G6.
Specific examples (specific example group G9) of the group represented by —S—(R905) described herein include
In which,
G1 is the “aryl group” described in the specific example group G1.
G2 is the “heterocycle group” described in the specific example group G2.
G3 is the “alkyl group” described in the specific example group G3.
G6 is the “cycloalkyl group” described in the specific example group G6.
Specific examples (specific example group G10) of the group represented by —N(R906)(R907) described herein include
In which,
G1 is the “aryl group” described in the specific example group G1.
G2 is the “heterocycle group” described in the specific example group G2.
G3 is the “alkyl group” described in the specific example grow G3.
G6 is the “cycloalkyl group” described in the specific example group G6.
Specific examples (specific example group G11) of the “halogen atom” described herein include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the “alkoxy group” described herein include a group represented by —O(G3), where G3 is the “alkyl group” described in the specific example group G3. The number of carbon atoms of the “unsubstituted alkoxy group” are 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise specified.
Specific examples of the “alkylthio group” described herein include a group represented by —S(G3), where G3 is the “alkyl group” described in the specific example group G3. The number of carbon atoms of the “unsubstituted alkylthio group” are 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise specified.
Specific examples of the “aryloxy group” described herein include a group represented by —O(G1), where G1 is the “aryl group” described in the specific example group G1. The number of ring carbon atoms of the “unsubstituted aryloxy group” are 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
Specific examples of the “arylthio group” described herein include a group represented by —S(G1), where G1 is the “aryl group” described in the specific example group G1. The number of ring carbon atoms of the “unsubstituted arylthio group” are 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise specified.
Specific examples of the “aralkyl group” described herein include a group represented by -(G3)-(G1), where G3 is the “alkyl group” described in the specific example group G3, and G1 is the “aryl group” described in the specific example group G1. Accordingly, the “aralkyl group” is one embodiment of the “substituted alkyl group” substituted by the “aryl group”. The number of carbon atoms of the “unsubstituted aralkyl group,” which is the “unsubstituted alkyl group” substituted by the “unsubstituted aryl group,” are 7 to 50, preferably 7 to 30, and more preferably 7 to 18, unless otherwise specified.
Specific example of the “aralkyl group” include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, a phenyl-t-butyl group, an α-naphthylmethyl group, a 1-α-naphthylethyl group, a 2-α-naphthylethyl group, a 1-α-naphthylisopropyl group, a 2-α-naphthylisopropyl group, a β-naphthylmethyl group, a 1-β-naphthylethyl group, a 2-β-naphthylethyl group, a 1-β-naphthylisopropyl group, and a 2-β-naphthylisopropyl group.
The substituted or unsubstituted aryl group described herein is, unless otherwise specified, preferably a phenyl group, a p-biphenyl group, a m-biphenyl group, an o-biphenyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl-4-yl group, a m-terphenyl-3-yl group, a m-terphenyl-2-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group, an o-terphenyl-2-yl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a fluorenyl group, a 9,9′-spirobifluorenyl group, a 9,9-diphenylfluorenyl group, or the like.
The substituted or unsubstituted heterocyclic group described herein is, unless otherwise specified, preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a benzimidazolyl group, a phenanthrolinyl group, a carbazolyl group (a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, or a 9-carbazolyl group), a benzocarbazolyl group, an azacarbazolyl group, a diazacarbazolyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, an azadibenzofuranyl group, a diazadibenzofuranyl group, a dibenzotiophenyl group, a naphthobenzothiophenyl group, an azadibenzothiophenyl group, a diazadibenzothiophenyl group, a (9-phenyl)carbazolyl group (a (9-phenyl)carbazol-1-yl group, a (9-phenyl)carbazol-2-yl group, a (9-phenyl)carbazol-3-yl group, or a (9-phenyl)carbazol-4-yl group), a (9-biphenyl)carbazolyl group, a (9-phenyl)phenylcarbazolyl group, a dipbenylcarbazole-9-yl group, a phenylcarbazol 9-yl group, a phenyltriazinyl group, a biphenylyltriazinyl group, diphenyltriazinyl group, a phenyldibenzofuranyl group, a phenyldibenzothiophenyl group, an indrocarbazolyl group, a pyrazinyl group, a pyridazinyl group, a quinazolinyl group, a cinnolinyl group, a phthalazinyl group, a quinoxalinyl group, a pyrrolyl group, an indolyl group, a pyrrolo[3,2,1-jk]carbazolyl group, a furanyl group, a benzofuranyl group, a thiophenyl group, a benzothiophenyl group, a pyrazolyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, an isothiazolyl group, a benzisothiazolyl group, a thiadiazolyl group, an isoxazolyl group, a benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, an indro[3,2,1-jk]carbazolyl group, a dibenzothiophenyl group, or the like.
The dibenzofuranyl group and the dibenzothiophenyl group as described above are specifically any group described below, unless otherwise specified.
In the formulas (XY-76) to (XY-79), XB is an oxygen atom or a sulfur atom.
The substituted or unsubstituted alkyl group described herein is, unless otherwise specified, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, or the like.
The “substituted or unsubstituted arylene group” descried herein refers to a group in which the above-described “aryl group” is converted into divalence, unless otherwise specified. Specific examples (specific example group G12) of the “substituted or unsubstituted arylene group” include a group in which the “aryl group” described in the specific example group G1 is converted into divalence. Namely, specific examples (specific example group G12) of the “substituted or unsubstituted arylene group” refer to a group derived from the “aryl group” described in specific example group G1 by removal of one hydrogen atom bonded to the ring carbon atoms thereof.
Specific examples (specific example group G13) of the “substituted or unsubstituted divalent heterocycle group” include a group in which the “heterocyclic group” described in the specific example group G2 is converted into divalence. Namely, specific examples (specific example group G13) of the “substituted or unsubstituted divalent heterocyclic group” refer to a group derived from the “heterocyclic group” described in specific example group G2 by removal of one hydrogen atom bonded to the ring atoms thereof.
Specific examples (specific example group G14) of the “substituted or unsubstituted alkylene group” include a group in which the “alkyl group” described in the specific example group G3 is converted into divalence. Namely, specific examples (specific example group G14) of the “substituted or unsubstituted alkylene group” refer to a group derived from the “alkyl group” described in specific example group G3 by removal of one hydrogen atom bonded to the carbon atoms constituting the alkane structure thereof.
The substituted or unsubstituted arylene group described herein is any group described below, unless otherwise specified.
In the formulas (XY-20) to (XY-29), (XY-83) and (XY-84), R906 is a substituent.
Then, m901 is an integer of 0 to 4, and when m901 is 2 or more, a plurality of R906 may be the same with or different from each other.
In the formulas (XY-30) to (XY-40), R909 is independently a hydrogen atom or a substituent. Two of R909 may form a ring by bonding with each other through a single bond.
In the formulas (XY-41) to (XY-46), R910 is a substituent.
Then, m902 is at integer of 0 to 6. When m902 is 2 or more, a plurality of R910 may be the same with or different from each other.
The substituted or unsubstituted divalent heterocyclic group described herein is preferably any group described below, unless otherwise specified.
In the formulas (XY-50) to (XY-60), R911 is a hydrogen atom or a substituent.
In the formulas (XY-65) to (XY-75), XB is an oxygen atom a a sulfur atom.
Herein, a case where “one a more sets of two or more groups adjacent to each other form a substituted or unsubstituted and saturated or unsaturated ring by bonding with each other” will be described by taking, as an example, a case of an anthracene compound represented by the following formula (XY-80) in which a mother skeleton is an anthracene ring.
For example, two adjacent to each other into one set when “one or more sets of two or more groups adjacent to each other form the ring by bonding with each other” among R921 to R930 include R921 and R922, R922 and R923, R923 and R924, R924 at R930, R930 and R925, R925 and R926, R926 and R927, R927 and R928, R928 and R929, and R929 and R921.
The above-described “one or more sets” means that two or mare sets of two groups adjacent to each other may simultaneously form the ring. For example, a case where R921 and R922 form a ring A by bonding with each other, and simultaneously R925 and R926 form a ring B by bonding with each other is represented by the following formula (XY-81).
A case where “two or more groups adjacent to each other” form a ring means than, for example, R921 and R922 form a ring A by bonding with each other, and R922 and R923 form a ring C by bonding with each other. A case where the ring A and ring C sharing R922 are formed, in which the ring A and the ring C are fused to the anthracene mother skeleton by three of R921 to R923 adjacent to each other, is represented by the following (XY-82).
The rings A to C formed in the formulas (XY-81) and (XY-82) are a saturated or unsaturated ring.
A term “unsaturated ring” means an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A term “saturated ring” means an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
For example, the ring A formed by R921 and R922 being bonded with each other, represented by the formula (XY-81), means a ring formed by a carbon atom of the anthracene skeleton bonded with R921, a carbon atom of the anthracene skeleton bonded with R922, and one or more arbitrary elements. Specific examples include, when the ring A is formed by R921 and R922, a case where an unsaturated ring is formed of a carbon atom at an anthracene skeleton bonded with R921, a carbon atom of the anthracene skeleton bonded with R922, and four carbon atoms, in which a ring formed by R921 and R922 is formed into a benzene ring. Further, when a saturated ring is formed, the ring is formed into a cyclohexane ring.
Here, “arbitrary elements” are preferably a C element, a N element, an O element and a S element. In the arbitrary elements (for example, a case of the C element or the N element), the bond(s) that is(are) not involved in the formation of the ring may be terminated by a hydrogen atom, or may be substituted by an arbitrary substituent. When the ring contains the arbitrary elements other than the C element, the ring to be formed is a heterocyclic ring.
The number of “one or more arbitrary elements” forming the saturated or unsaturated ring is preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and further preferably 3 or more and 5 or less.
As specific examples of the aromatic hydrocarbon ring, a structure in which the aryl group described in specific example group G1 is terminated with a hydrogen atom may be mentioned.
As specific examples of the aromatic heterocyclic ring, a structure in which the aromatic heterocyclic group described in specific example group G2 is terminated with a hydrogen atom may be mentioned.
As specific examples of the aliphatic hydrocarbon ring, a structure in which the cycloalkyl grow described in specific example group G6 is terminated with a hydrogen atom may be mentioned.
When the above-described “saturated or unsaturated ring” has a substituent, the substituent is an “arbitrary substituent” as described below, for example. When the above-mentioned “saturated or unsaturated ring” has a substituent, specific examples of the substituent refer to the substituents described in above-mentioned “the substituent described herein”.
In one embodiment of the this specification, the substituent (hereinafter, referred to as an “arbitrary substituent” in several cases) in the case of the “substituted or unsubstituted” is a group selected from the group consisting of
In one embodiment, the substituent in the case of “substituted or unsubstituted” is a group selected from the group consisting of
In one embodiment, the substituent in the case of “substituted or unsubstituted” is a group selected from the group consisting of
Specific examples of each group of the arbitrary substituent described above are as described above.
Herein, unless otherwise specified, the saturated or unsaturated ring (preferably substituted or unsubstituted and saturated or unsaturated five-membered or six-membered ring, more preferably a benzene ring) may be formed by the arbitrary substituents adjacent to each other.
Herein, unless otherwise specified, the arbitrary substituent may further have the substituent. Specific examples of the substituent that the arbitrary substituent further has include to the ones same as the arbitrary substituent described above.
The organic EL device according to one aspect of the invention comprises a cathode, an anode and an emitting layer deposed between the cathode and the anode, and it is characterized in that the emitting layer comprises a compound represented by the following formula (1) and one or more compounds selected from the group consisting of a compound represented by formula (11), a compound represented by formula (21), a compound represented by formula (31), a compound represented by formula (41), a compound represented by formula (51), a compound represented by formula (61), a compound represented by formula (71) and a compound represented by formula (81).
Each compound is described later.
The organic EL device according to one aspect of the invention exhibits high device performance by possessing the above-mentioned constitution. Specifically, it is possible to provide an organic EL device which is able to simultaneously satisfy both characteristics of a low CIEy value and a long life.
According to one aspect of the present invention, a method for improving a performance of an organic EL device can also be provided. The method is characterized in that the compound represented by the formula (1) and one or more compounds selected from the group consisting of the compounds represented by each of formulas (11) to (81) are used in combination in the emitting layer of the organic EL device. Specifically, the method can improve an organic EL device performance as compared with the case where a compound having the same structure as formula (1) except that only protium atoms are contained as hydrogen atoms (hereinafter also referred to as “protium compound”) is used as a host material. The case where the protium compound is used means that a host material in an emitting layer consists essentially of the protium compound (the ratio of the protium compound to the sum of the protium compound and the compound represented by formula (1) is 90 mol % or more, 95 mol % or more, or 99 mol % or more).
That is, it is possible to increase a performance of an organic EL device by, instead of a podium compound or in addition to a protium compound, using a compound obtained by replacing at least one protium atoms on an anthracene skeleton of the protium compound with a deuterium atom (a compound represented by formula (1)) as a host material.
A schematic outline of the organic EL device of one aspect of the invention is explained by reference to
The organic EL device 1 according to one aspect of the invention comprises substrate 2, anode 3, emitting layer 5, cathode 10, organic layer 4 disposed between the anode 3 and the emitting layer 5, and organic layer 6 disposed between the emitting layer 5 and the cathode 10.
The compound represented by the formula (1) and one or more compounds selected from a group consisting of a compound represented by formula (11), a compound represented by formula (21), a compound represented by formula (31), a compound represented by formula (41), a compound represented by formula (51), a compound represented by formula (61), a compound represented by formula (71) and a compound represented by formula (81) are contained in emitting layer 5 disposed between the anode 3 and the cathode 10. These compounds may be used singly or in combination of two or more.
The compound represented by the formula (1) is explained below.
In the formula (1),
R1 to R6 are independently
R901 to R907 are independently
when two or more of R901 to R907 exist, two or more of R901 to R907 may be the same with or different from each other;
at least one of R1 to R8 is a deuterium atom;
two or more adjacent groups of R1 to R4 do not form a ring by bonding with each other; and
two a more adjacent groups of R5 to R8 do not form a ring by bonding with each other;
L1 and L2 are independently
Ar1 and Ar2 are independently
when L1, L2, Ar1 and Ar2 have a substituent, the substituent is
All of R1 to R8 may be deuterium atoms or a part of them (e.g., one or two of R1 to R8) may be deuterium atoms.
R1 to R8 that are not deuterium atoms am preferably hydrogen atoms (protium atoms).
In one embodiment, at least one hydrogen atom contained in one or more groups selected from a group consisting of L1 and L2 is a deuterium atom. All hydrogen atoms contained in one or more groups selected from a group consisting of L1 and L2 may be a deuterium atom. In more detail, in one embodiment, one or more groups selected from the group consisting of L1 and L2 are
In one embodiment, L1 and L2 are independently a single bond, a substituted or unsubstituted phenylene group, or a naphthylene group. It is preferable that at least one of L1 and L2 be a single bond.
In one embodiment, at least one hydrogen atom contained in one or more groups selected from a group consisting of Ar1 and Ar2 is a deuterium atom. All hydrogen atoms contained in one or more groups selected from a group consisting of Ar1 and Ar2 may be a deuterium atom. In more detail, in one embodiment, one or more groups selected from the group consisting of Ar1 and Ar2 are
In one embodiment, Ar1 and Ar2 are independently a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted phenanthryl group.
In one embodiment, the compound represented by the formula (1) is represented by the following formula (1A):
wherein in the formula (1A), R11 to R18 are independently a hydrogen atom, and at least one of R11 to R18 is a deuterium atom;
adjacent two or more among R11 to R14 are not bonded with each other to form a ring, and adjacent two or more among R15 to R18 are not bonded with each other to form a ring;
L11 and L12 are independently a single bond, an unsubstituted phenylene group, or an unsubstituted naphthylene group; and
Ar11 and Ar12 are independently an unsubstituted phenyl group or an unsubstituted naphthyl group.
In one embodiment, in the formula (1A), at least two of R11 to R18 are deuterium atoms.
In one embodiment, in the formula (1A), R11 to R18 are all deuterium atoms.
In one embodiment, in the formula (1A), at least one hydrogen atom contained in one or more selected from the group consisting of L11 and L12 is a deuterium atom.
In one embodiment, in the formula (1A), at least one hydrogen atom contained in one or mare selected from the group consisting of Ar11 and Ar12 is a deuterium atom.
Existence of a deuterium atom in the compound is confirmed by Mass Spectrometry or 1H-NMR Spectrometry. The bonding position of a deuterium atom in the compound is identified by 1H-NMR Spectrometry. In concrete terms, it is confirmed as follows.
If it is identified that, by Mass Spectrometry, a molecular weight of a target compound is greater by “one” than a molecular weight of a corresponding compound in which all hydrogen atoms are protium atoms, it is confirmed that one deuterium atom exists in the target compound. Further, the number of deuterium atoms in a molecule can be confirmed by an integration value obtained by 1H-NMR analysis on the target compound, since no signal is observed by performing 1H-NMR analysis on a deuterium atom. The bonding position of a deuterium can be identified by performing 1-NMR analysis on the target compound and assigning signals.
It is preferable that, in the compound represented by the formula (1), the content ratio of a compound in which only protium atoms are contained as hydrogen atoms (a compound having the same structure as formula (1) except that only protium atoms are contained as hydrogen atoms (protium compound)) is 99 mol % or less. The content ratio of the protium compound is confirmed by Mass Spectrometry.
In one embodiment, the emitting layer of the organic EL device according to one aspect of the invention contains the compound represented by the formula (1) and a protium compound, and the content ratio of the latter to the total thereof is 99 mol % or less.
In one embodiment, the emitting layer of the organic EL device according to one aspect of the invention contains the compound represented by the formula (1) and a protium compound, and the content ratio of the former to the total thereof is 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more, 95 mol % or more, 99 mol % or more, or 100 mol %.
The compound represented by the formula (1) i.e., a compound used in the scope of the present invention can be synthesized in accordance with the synthesis process described in Examples by using publicly known alternative reactions or materials corresponding to a target compound.
Examples of the compound represented by formula (1) include the following compounds. In the following example compounds, D represents a deuterium atom.
The compound represented by the (11) is explained below.
In the formula (11),
one or more pairs of two or more adjacent groups of R101 to R110 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
at least one of R101 to R110 is a monovalent group represented by the formula (12);
R101 to R110 that do not form the substituted or unsubstituted, saturated or unsaturated ring and that are not a monovalent group represented by the following formula (12) are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (12), Ar101 and Ar102 are independently
L101 to L103 are independently
In the formula (11), it is preferable that two of R101 to R110 be the group represented by the formula (12).
In one embodiment, the compound represented by the formula (11) is represented by the following formula (13):
wherein in the formula (13), R111 to R118 are the same as R101 to R110 that is not a monovalent group represented by the formula (12) in the formula (11). Ar101, Ar102, L101, L102 and L103 are as defined in the formula (12).
In the formula (11), L101 is preferably a single bond and L102 and L103 are preferably a single bond.
In one embodiment, the compound represented by the formula (11) is represented by the formula (14) or (15):
wherein in the formula (14), R111 to R118 are as defined in the formula (13), Ar101, Ar102, L102 and L103 are as defined in the formula (12);
wherein in the formula (15), R111 to R118 are as defined in the formula (13), Ar101 and Ar102 are as defined in the formula (12).
In the formula (11) and formula (12), it is preferable that at least one Ar101 and Ar102 be the group represented by the following formula (16):
wherein in the formula (16),
X101 is an oxygen atom or a sulfur atom;
One or more pairs of two or more adjacent groups of R121 to R127 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring:
R121 to R127 that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R901 to R907 are as defined in the formula (1).
It is preferable that X101 be an oxygen atom.
It is preferable that at least one of R121 to R127 be
It is preferable that in the formula (11) and formula (12), Ar101 be a group represented by the formula (16) and Ar102 be a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, the compound represented by the (11) is represented by the following formula (17):
wherein in the formula (17), R111 to R118 are as defined in the formula (13), and R121 to R127 are as defined in the formula (16);
R131 to R135 are independently
As the compound represented by the formula (11), the following compounds can be given as specific examples, for example. In the following example compounds, Me represents a methyl group.
The compound represented by the formula (21) is explained below.
In the formula (21),
Zs are independently CRa or N;
A1 ring and A2 ring are independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms;
when a plurality of Ras exist, two or more adjacent groups of Ra are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
when a plurality of Ras exist, one or more pairs of two or more adjacent groups of Rb are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
when a plurality of Ras exist, one or more pairs of two or more adjacent groups of Rc are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
n21 and n22 are independently an integer of 0 to 4;
Ra to Rc that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
The “aromatic hydrocarbon ring” of A1 ring and A2 ring has the same structure as the compound obtained by introducing a hydrogen atom into the “aryl group” described above.
The “aromatic hydrocarbon ring” of the A1 ring and the A2 ring contains two carbon atoms in the fused bicyclic structure at the center of the formula (21) as ring atoms. Examples of “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms” include compounds in which a hydrogen atom is introduced into the “aryl group” described in the example group G1.
The “heterocyclic ring” of A1 ring and A2 ring has the same structure as the compound obtained by introducing a hydrogen atom into the “heterocyclic group” described above. The “heterocyclic ring” of the A1 ring and the A2 ring contains two carbon atoms in the fused bicyclic structure at the center of the formula (21) as ring atoms. Examples of “substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms” include compounds in which a hydrogen atom is introduced into the “heterocyclic group” descried in the example group G2.
Rb is bonded to one of carbon atoms which form the aromatic hydrocarbon ring of A1 ring, or one of atoms which form the heterocycle of A1 ring.
Rc is bonded to one of carbon atoms which form the aromatic hydrocarbon ring of A2 ring, or one of atoms which form the heterocycle of A2 ring.
It is preferable that at least one (preferably two) of Ra to Rb be a group represented by the following formula (21a):
-L201-Ar201 (21a)
wherein in the formula (21a),
L201 is
Ar201 is
wherein in the formula (21b),
L211 and L212 are independently
Ar211 and Ar212 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring; and
Ar211 and Ar212that do not form a substituted or unsubstituted, saturated or unsaturated ring are independently
a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or
a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the compound represented by the formula (21) is represented by the following formula (22):
wherein in the formula (22),
one or more pairs of two or more adjacent groups of R201 to R211 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring;
R201 to R211 do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R901 to R907 are as defined in the formula (1).
It is preferable that at least one (preferably two) of R201 to R211 be the group represented by the formula (21a), it is preferable that R204 and R211 be the group represented by the formula (21a).
In one embodiment, the compound represented by the formula (21) is a compound obtained by bonding the structure represented by the following formula (21-1) or (21-2) to A1 ring. In one embodiment, the compound represented by the formula (22) is a compound obtained by bonding the structure represented by the following formula (21-1) or (21-2) to the ring to which R204 to R207 bonds to.
In the formula (21-1), two bonds shown by * independently bond to a ring carbon atom in the aromatic hydrocarbon ring or a ring atom in the heterocyclic group in A1 ring in the formula (21), or bond to one of R204 to R207 in the formula (22);
wherein in the formula (21-2), three bonds shown by * independently bond to a ring carbon atom in the aromatic hydrocarbon ring or a ring atom in the heterocyclic group in A1 ring in the formula (21), or bond to one of R204 to R207 in the formula (22);
One or more pairs of two or more adjacent groups of R221 to R227 and R221 to R230 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
R221 to R227 and R231 to R239 that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R901 to R907 are as defined in the formula (1)
In one embodiment, the compound represented by the formula (21) is a compound represented by the following formula (21-3), (21-4), or (21-5):
wherein in the formulas (21-3), (21-4) and (21-5),
A1 ring is as defined in the formula (21);
R2401 to R2407 are the same as R221 to R227 in the formulas (21-1) and (21-2);
R2410 to R2417 are the same as R201 to R211 in the formula (22); and the two R2417s may be the same or different.
In one embodiment, the substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms of A1 ring in the formula (21-5) is a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted fluorene ring.
In one embodiment the substituted or unsubstituted heterocycle having 5 to 50 ring atoms of A1 ring in the formula (21-5) is a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted carbazole ring, or a substituted or unsubstituted dibenzothiaphene ring.
In one embodiment, the compound represented by the formula (21) or (22) is selected from the group consisting of the compounds represented by the following formulas (21-6-1) to (21-6-7):
wherein in the formulas (21-6-1) to (21-6-7),
R2421 to R2427 are the same as R221 to R227 in the formulas (21-1) and (21-2);
R2430 to R2437 and R2441 R2444 are the same as R201 to R211 in the formula (22);
X is O, NR901, or C(R902)(R903); and
R901 to R903 are as defined lithe formula (1).
In one embodiment, in the compound represented by the formula (22), one or more pairs of two or more adjacent groups of R201 to R211 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring. This embodiment is described in the following formula (25).
The compound represented by the formula (25) is explained below.
In the formula (25),
two or more pairs selected from a group consisting of R251 and R252, R252 and R253, R254 and R255, R255 and R256, R256 and R257, R258 and R260, R258 and R260, and R260 and R261 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring;
Provided that the pair of R251 and R252 and the pair of R252 and R253 do not form a ring simultaneously, the pair of R254 and R255 and the pair of R255 and R256 do not form a ring simultaneously, the pair of R255 and R256 and the pair of R256 and R257 do not form a ring simultaneously; the pair of R256 and R260 and the pair of R260 and R260 do not form a ring simultaneously; and the pair of R250 and R260 and the pair of R260 and R261 do not form a ring simultaneously;
When two or more rings are formed by R251 to R261, the rings may be the same or different;
R251 to R261 that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R901 to R907 are as defined in the formula (1).
In the formula (25), Rn and Rn+1 (n is an integer selected from 251, 252, 254 to 256 and 258 to 260) bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring together with two ring carbon atoms to which Rn and Rn+1 bond with. The ring is preferably configured with atoms selected from C atom, O atom, S atom and N atom, and the number of atoms is preferably 3 to 7, more preferably 5 or 6.
The number of the above-described ring structures in the compound represented by the formula (25) is, for example, 2, 3 or 4. Two or more ring structures may exist in the same benzene ring of the main skeleton in the formula (25), or may exist in different benzene rings. For example, the compound has three ring structures, one ring structure may exist in each of the three benzene rings in the formula (25).
As the above-mentioned ring structure in the compound represented by the formula (25), structures represented by the following formulas (251) to (260) can be given, for example.
In the formulas (251) to (257),
each of *1 and *2, *3 and *4, *5 and *6, *7 and *8, *9 and *10, *11 and *12, and *13 and *14 represents two ring carbon atoms to which Rn and Rn+1 bond, and Rn may bond to either one of the two mg carbon atoms of *1 and *2, *3 and *4, *5 and *6, *7 and *8, *9 and *10, *11 and *12, and *13 and *14:
X2501 is C(R2512) (R2513), NR2514, O or S;
One or more pairs of two or more adjacent groin of R2501 to R2506 and R2512 to R2513 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring; and
R2501 to R2514 that do not form a substituted or unsubstituted saturated or unsaturated ring are the same as R251 to R261.
In the formulas (258) to (260),
each of *1 and *2, and *3 and *4 represents two ring carbon atoms to which Rn to Rn+1 bond, and Rn may bond to either one of the tom ring carbon atoms of *1 and *2, or *3 and *4;
X2501 is C(R2512)(R2513), NR2514, O or S;
One or more pairs of two or more adjacent groups of R2515 to R2525 bond to each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring; and
R2515 to R2521 and R2522 to R2525 that do not form a substituted or unsubstituted saturated or unsaturated ring are the same as R251 to R261.
In the formula (25), it is preferable that at least one of R252, R254, R255, R260 and R261 (preferably at least one of R252, R255, and R260, more preferably R252) be a group which does not form a ring.
In the formulas (261) to (264),
Rds are independently
X is C(R901)(R902), NR903, O, or S;
R901 to R907 are as defined in the formula (1); and
p1 is independently an integer of 0 to 5, p2 is independently an integer of 0 to 4, p3 is an integer of 0 to 3, and p4 is an integer of 0 to 7.
In one embodiment, the compound represented by the formula (25) is represented by the following formulas (25-1) to (25-6):
wherein in the formulas (25-1) to (25-6), ring d to ring i are independently a substituted or unsubstituted, saturated or unsaturated ring; and R251 to R261 are the same as defined in the formula (25).
In one embodiment, the compound represented by the formula (25) is represented by the following formulas (25-7) to (25-12):
wherein in the formulas (25-7) to (25-12), ring d to ring f, ring k, and ring j are independently a substituted or unsubstituted, saturated or unsaturated ring; and R251 to R261 are the same as defined in the formula (25).
In one embodiment, the compound represented by the formula (25) is represented by the following formulas (25-13) to (25-21):
wherein in the formulas (25-13) to (25-21), ring d to ring k are independently a substituted or unsubstituted, saturated or unsaturated ring; and R251 to R261 are the same as defined in the formula (25).
As a substituent in the case where the ring g or ring h further has a substituent,
In one embodiment, the compound represented by the formula (25) is represented by one of the following formulas (25-22) to (25-25):
wherein in the formulas (25-22) b (25-25), X250 is independently C(R901)(R902), NR903, O or S; R251 to R261, and R271 to R278 are he same as R251 to R261 in the formula (25); and R901 to R903 are as defined in the formula (1).
In one embodiment, the compound represented by the formula (25) is represented by the following formula (25-26):
wherein in the formula (25-26), X250 is C(R901)(R902), NR903, O or S; R253, R254, R257, R256, R261, and R271 to R262 are the same as R251 to R261 in the formula (25); and R901 to R903 are as defined in the formula (1).
As the compound represented by the formula (21), the following compounds can be shown for example. In the following example compounds, Me represents methyl group.
The compound represented by the formula (31) is explained below. The compound represented by formula (31) is a compound corresponding to the compound represented by the formula (21-3).
In the formula (31),
one or more pairs of two or more adjacent groups of R301 to R307 and R311 to R317 form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
R301 to R307 and R311 to R317 that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently
R321 and R322 are independently
R901 to R907 are as defined in the formula (1).
Example of “One pair of two or more adjacent groups of R301 to R307 and R311 to R317” is pairs of R301 and R302, R302 and R303R303 and R304, R305 and R306, R306 and R307, and R301, R302 and R303, and the like.
In one embodiment, at least one of R301 to R307 and R311 to R317, preferably two of R301 to R307 and R311 to R317 is a group represented by —N(R906)(R907).
In one embodiment, R301 to R307 and R311 to R317 are independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the compound represented by the formula (31) is a compound represented by the following formula (32):
wherein into formula (32),
one or more pairs of two or more adjacent groups of R331 to R334 and R341 to R344 form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring;
R331 to R334 and R341 to R344 that do not form the substituted or unsubstituted, saturated or unsaturated ring and R351 and R352 are independently
R351 to R354 are independently
In one embodiment, the compound represented by the formula (31) is a compound represented by the formula (33):
wherein in the formula (33), R351, R352, and R361 to R364 are as defined in the formula (32).
In one embodiment, the compound represented by the formula (31) is a compound represented by the formula (34) or (35):
wherein in the formulas (34) and (35),
R361 to R364 are as defined in the formula (32):
one or more pairs of two or more adjacent groups of R371 to R377 and R380 to R386 form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted saturated or unsaturated ring; and
R371 to R377 and R380 to R386 that do not form the substituted or unsubstituted, saturated or unsaturated ring and R367 are independently
In one embodiment, the compound represented by the formula (31) is a compound represented by the formula (34-2) or (35-2):
wherein in the formulas (34-2) and (35-2), R361 to R364, R375 to R377 and R364 to R367 are as defined in the formulas (34) and (35).
In one embodiment, R361 to R364 in the formulas (32), (33), (34), (35), (34-2) and (35-2) are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably a substituted or unsubstituted phenyl group).
In one embodiment, R321 and R322 in the formula (31) and R351, R352 and R367 in the formulas (32), (33), (34), (35), (34-2) and (35-2) are independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms (preferably a substituted or unsubstituted phenyl group).
In one embodiment, the compound represented by the formula (31) is one or more compounds selected from the group consisting of the following formulas (32-11), (34-11) and (35-11):
wherein in the formulas (32-11), (34-11) and (35-11),
one or more pairs of two or more adjacent groups of R3301 to R3307 and R3311 to R3317 form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
R3301 to R3307 and R3311 to R3317 that do not form the substituted or unsubstituted, saturated a unsaturated ring, and R3331 are independently
two R3331s may be the same with or different from each other; and
R3321 to R3324 are independently
In one embodiment, the one or more compounds selected from the group consisting at the formulas (32-11), (34-11) and (35-11) is one or more compounds selected from a group consisting of the following formulas (32-12), (34-12) and (35-12):
wherein in the formulas (32-12), (34-12) and (35-12), R3321 to R3324 and R3331 are as defiled in the formulas (32-11), (34-11) and (35-11).
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), R3321 to R3324 are independently a substituted a unsubstituted phenyl group.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), two R3331s are independently a hydrogen atom.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), the substituent in the case of “substituted or unsubstituted” is selected flan the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 ring carbon atoms, and a monovalent heterocyclic group having 5 to 20 ring atoms.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), the substituent in the case of “substituted or unsubstituted” is an alkyl group having 1 to 5 carbon atoms.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), R3321 to R3324 are independently a substituted or unsubstituted phenyl group, and two R3331s are independently a hydrogen atom.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), R3321 to R3324 are independently a substituted a unsubstituted phenyl group, two R3331s are independently a hydrogen atom, and the substituent in the case of “substituted or unsubstituted” is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 ring carbon atoms, and a monovalent heterocyclic group having 5 to 20 ring atoms.
In one embodiment, in the formulas (32-11), (34-11), (35-11), (32-12), (34-12) and (35-12), R3321 to R3324 are independently a substituted or unsubstituted phenyl group, two R3331s are independently a hydrogen atom, and the substituent in the case of “substituted or unsubstituted” is an alkyl group having 1 to 5 carbon atoms.
In one embodiment, in the compound represented by the formula (31), one or more pairs of two or more adjacent groups of R301 to R307 and R311 to R317 form a substituted or unsubstituted, saturated or unsaturated ring.
In one embodiment, the compound represented by he formula (31) is one or more compounds selected from the group consisting of the following formulas (36-1) to (36-6):
wherein in the formulas (36-1) b (36-6),
one or more pairs of two or more adjacent groups of R3605 to R3607, R3615 to R3617 and R3631 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form the ring;
one or more pairs of two or more adjacent groups of R3601 to R3604, R3611 to R3614 and R3621 to R3628 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form the ring;
R3601 to R3607, R3611 to R3617, R3621 to R3626 and R3631 that do not form the ring are independently
R901 to R907 are independently
when two or more of R901 to R907 exist, two a more of R901 to R907 may be the same with or different from each other;
X1 is selected from O, S and N(R3641), and two X1s may be the same with or afferent from each other;
R3641 and one or more groups selected from R3601 to R3604, R3611 to R3614, R3624 and R3626 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form the ring; and
R3641 that do not form the ring is a hydrogen atom,
In one embodiment, the compound represented by the formula (31) is a compound represented by the Formula (36-1) or (36-2). In one embodiment, the compound represented by the formula (31) is a compound represented by the formula (36-1).
In one embodiment, in the compound represented by the formulas (36-1) to (36-6), two R3631s are phenyl groups.
In one embodiment, in the compound represented by the formulas (36-1) to (36-6), X1 is N(R3641).
In one embodiment, in the compound represented by the formulas (36-1) to (36-6), R3641 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, the compound represented by the formula (31) is a compound represented by the following formula (36-1-1):
wherein in the formula (36-1-1),
one or more pairs of two or more adjacent groups of R3001, R3002, R3005 to R3007, R3010, R3011, R3014 to R3016 and R3031 to R3034 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form the ring;
Xas are independently selected from O, S and N(R3035);
R3035 and R3031 bond with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form the ring; and
R3001, R3002, R3005 to R3007, R3010, R3011, R3014 to R3016 and R3031 to R3035 that do not form the ring and R3021 and R3022 are independently
In one embodiment, a substituent in the case of “substituted or unsubstituted” in the formulas (31) to (35), (34-2), (35-2), (32-11), (34-11), (35-11), (32-12), (34-12), (35-12), (36-1) to (36-6) and (36-1-1) is
As the compound represented by the formula (31), the following compounds can be given for example. In the following example compounds, Me represents methyl group.
The compound represented by the formula (41) is explained below.
In the formula (41),
a ring, b ring and c ring are independently
R401 and R402 are independently bonded to the a ring, the b ring or the c ring to form a substituted or unsubstituted heterocycle ring or do not form a substituted or unsubstituted heterocyclic ring;
R401 and R402 that do not form the substituted or unsubstituted heterocyclic ring are independently
The a ring, b ring and c ring are rings (a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms) fuse to the fused bicyclic structure composed of B atom and two N atoms in the center of the formula (41).
The “aromatic hydrocarbon ring” of the a ring, the b ring and the c ring has the same structure as the compound obtained by introducing a hydrogen atom into the “aryl group” described above. The “aromatic hydrocarbon ring” of the a ring contains three carbon atoms in the fused bicyclic structure in the center of the formula (41) as ring atoms. The “aromatic hydrocarbon ring” of the b ring and the c ring contain two carbon atoms in the fused bicyclic structure in the center of the formula (41) as ring atoms. As examples of “substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms”, compounds in which a hydrogen atom is introduced into the “aryl group” described in the group G1 and the like can be given.
The “heterocyclic ring” of the a ring, the b ring and the c ring has the same structure as the compound obtained by introducing a hydrogen atom into the “heterocyclic group” described above. The “heterocyclic ring” of the a ring contains three carbon atoms in the fused bicycle structure in the center of the formula (41) as ring atoms. The “heterocyclic ring” of the b ring and the c ring contain two carbon atoms in the fused bicycle structure in the center of the formula (41) as ring atoms. As examples of “substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms”, compounds in which a hydrogen atom is introduced into the “heterocyclic group” described in the group G2.
R401 and R402 may be independently bonded to the a ring, the b ring or the c ring to form a substituted or unsubstituted heterocycle ring. This heterocycle ring contains the nitrogen atom in the fused bicyclic structure in the center of the formula (41). This heterocyclic ring may contain a heteroatom other than the nitrogen atom. “R401 and R402 are bonded to the a ring, the b ring or the c ring” means, specifically, an atom forming the a ring, the b ring or the c ring is bonded to an atom forming R401 and R402. For example, it is possible that R401 is banded to the a ring to form a nitrogen-containing heterocyclic ring having a two-ring fused structure (or three or more rings fused structure) in with a ring containing R401 and the a ring are fused.
The same applies to the case where R401 is bonded to the b ring, R402 is bonded to the a ring, and R402 is bonded to the c ring.
In one embodiment, the a ring, the b ring and the c ring in the formula (41) are independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms.
In one embodiment, the a ring, the b ring and the c ring in the formula (41) are independently a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring.
In one embodiment, R401 and R402 in the formula (41) are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms, and preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, the compound represented by the formula (41) is a compound represented by the following formula (42):
wherein in the formula (42),
R401A is bonded with one or more groups selected from R411 or R421 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocycle ring; R402A is bonded with one or more group selected from R413 or R414 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocycle ring;
R401A and R402A that do not form a substituted or unsubstituted heterocyclic ring are independently
One or more pairs of two or more adjacent groups of R411 to R421 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
R411 to R421 that do form the substituted or unsubstituted heterocyclic ring or the substituted or unsubstituted, saturated or unsaturated ring are independently
R901 to R907 are as defined in the formula (1).
R401A and R402A in the formula (42) correspond to R401 and R402 in the formula (41). R401A and R411 may be bonded with each other to form a nitrogen-containing heterocyclic ring having two-ring fused structure (or tree or more rings fused structure) which is a fused ring of a ring containing R401A and R411 and the benzene ring of the a ring, for example. As examples of the nitrogen-containing heterocyclic ring, compounds correspond to nitrogen-containing heterocyclic group having two or more ring fused structure in the group G2 can be given. The same applies to the cases where R401A and R412 are bonded, R402A and R413 are bonded, and R402A and R414 are bonded.
One or more pairs of two or more adjacent groups of R411 to R421 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring. For example, R411 and R412 are bonded to form a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring or the like which fuses to the six-membered ring to which R411 and R412 bond, and the formed fused ring is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring.
In one embodiment, R411 to R421 that do not contribute to form a ring are independently 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 monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, R411 to R421 that do not contribute to form a ring are independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, R411 to R421 that do not contribute to form a ring are independently a hydrogen atom of a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, R411 to R421 that do not contribute to form a ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and at least one of R411 to R421 is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, the compound represented by the formula (42) is a compound represented by the following formula (43):
wherein in the formula (43),
R431 is bonded with R446 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocyclic ring; R433 is bonded with R447 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocyclic ring; R434 is bonded with R451 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocyclic ring; R441 is bonded with R442 to form a substituted or unsubstituted heterocyclic ring, or does not form a substituted or unsubstituted heterocyclic ring;
One or more pairs of two or more adjacent groups of R431 to R451 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
R431 to R451 that do not form a substituted or unsubstituted heterocyclic ring are independently
R901 to R907 are as defined in the formula (1).
R431 may bond to R446 to form a substituted or unsubstituted heterocyclic ring. For example, R431 may bonds with R446 to form a nitrogen-containing heterocyclic ring with three or more fused rings of the benzene ring to which R46 bond, a nitrogen-containing ring and the benzene ring of the a ring. As examples of the nitrogen-containing heterocyclic ring, compounds correspond to nitrogen-containing heterocyclic group having three or more ring fused structure in the group G2 can be given. The same applies to the cases where R433 and R447 are bonded, R434 and R451 are bonded, and R441 and R442 are bonded.
In one embodiment, R431 to R451 that do not contribute to form a ring are independently, 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 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, R431 to R451 that do not contribute to form a ring are independently, a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms.
In one embodiment, R431 to R451 that do not contribute to form a ring are independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, R431 to R451 that do not contribute to form a ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and at least one of R431 to R451 is a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, the compound represented by the formula (43) is a compound represented by the following formula (43A):
wherein in the formula (43A),
R461 is
R462 to R465 are independently
In one embodiment, R461 to R465 are independently 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 one embodiment, R461 and R465 are independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, the compound represented by the formula (43) is a compound represented by the following formula (43B):
wherein in the formula (43B),
R471 and R472 are independently,
R473 to R475 are independently,
R906 and R907 are as defined in the formula (1).
In one embodiment, the compound represented by the formula (43) is the compound represented by the following formula (43B′):
wherein in the formula (43B′), R472 to R475 are as defined in the formula (43B).
In one embodiment, at least one of R471 to R475 is
In one embodiment,
R472 is
R471 and R473 to R475 are independently
In one embodiment, the compound represented by the formula (43) is a compound represented by the formula (43C):
wherein in the formula (43C),
R481 and R482 are independently
R483 to R486 are independently
In one embodiment, the compound represented by the formula (43) is the compound represented by the following formula (43C′):
wherein in the formula (43C′), R483 to R486 are as defined in the formula (43C).
In one embodiment, R481 to R486 are independently 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 one embodiment, R481 to R486 are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, the compound represented by the formula (43) is the compound represented by the following formula (43D):
wherein in the formula (43D), R4611 is a hydrogen atom, an unsubstituted alkyl group including 1 to 6 carbon atoms, an unsubstituted cycloalkyl group inducing 3 to 10 ring carbon atoms, —Si(R911)(R912)(R913), or —N(R914)(R915);
R4612 to R4615 are independently an unsubstituted alkyl group inducing 1 to 6 carbon atoms, an unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, or —Si(R911)(R912)(R913);
R911 to R913 are independently an unsubstituted alkyl group including 1 to 6 carbon atoms or an unsubstituted aryl group including 6 to 18 ring carbon atoms; and
R914 to R913 are independently an unsubstituted aryl group having 6 to 18 ring carbon atoms.
In one embodiment, in the formula (43D), R4611 is a hydrogen atom, an unsubstituted alkyl group including 1 to 6 carbon atoms, or —N(R914)(R915).
In one embodiment, in the formula (43D), R4612 to R4615 are independently an unsubstituted alkyl group including 1 to 6 carbon atoms or an unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms.
In one embodiment, in the formula (43D), R4611 is —N(R914)(R915), and R4612 to R4615 are independently an unsubstituted alkyl group including 1 to 6 carbon atoms.
In one embodiment, in the formula (43D), R4611 is an unsubstituted alkyl group including 1 to 6 carbon atoms, and R4612 to R4615 are independently an unsubstituted alkyl group including 1 to 6 carbon atoms.
In one embodiment, in the formula (43D), R4611 is a hydrogen atom, and R4612 to R4615 are independently an unsubstituted alkyl group including 1 to 6 carbon atoms or an unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms.
In one embodiment, in the formula (43D), at least one hydrogen atom contained in one or more selected from the group consisting of R914 and R915 is a deuterium atom.
The compound represented by the formula (41) can be synthesized by the following method: An intermediate is obtained by bonding the a ring, the b ring and the c ring with linking groups (a group containing N—R1 and a group containing N—R2) (first reaction), and a final compound is obtained by bonding the a ring, the b ring and the c ring with a linking group (a group containing B) (second reaction). In the first reaction, an amination reaction such as Buchwald-Hartwig reaction can be applied. In the second reaction, tandem hetero-Friedel-Crafts reaction or the like can be applied.
Examples of the compound represented by the formula (41) are described below. They are just exemplified compounds and the compound represented by the formula (41) is not limited to the following examples. In the following example compounds, Me represents methyl group, and tBu represents tert-butyl group.
The compound represented by the formula (51) is explained below.
In the formula (51),
r ring is a ring represented by the formula (52) or formula (53) which is fused to an adjacent ring at an arbitrary position;
q ring and s ring are independently a ring represented by the formula (54) which is fused to an adjacent ring at an arbitrary position;
p ring and t ring are independently a ring represented by the formula (55) or the formula (56) which is fused to an adjacent ring at an arbitrary position;
when a plurality of R501s exist, adjacent R501s are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring, or do not form a substituted or unsubstituted, saturated or unsaturated ring;
X501 is an oxygen atom, a sulfur atom, or NR502;
R501 and R502 that do not form the substituted or unsubstituted saturated or unsaturated ring are a hydrogen atom,
R901 to R907 are as defined in the formula (1);
Ar501 and Ar502 are independently
L501 is
m1 is independently an integer of 0 to 2, m2 is independently an integer of 0 to 4, m3s are independently an integer of 0 to 3, and m4s are independently an integer of 0 to 5; when a plurality of R501s exist, R501s may be the same or different.
In the formula (51), each of the p ring to the t ring is fused to an adjacent ring by sharing two carbon atoms. The position and direction of fusing are not limited, and condensation is possible at any position and direction.
In one embodiment, in the formula (52) or (53) of the r ring, R501 is a hydrogen atom.
In one embodiment, the compound represented by the formula (51) is represented by any one of the following formulas (51-1) to (51-6):
wherein in the formulas (51-1) to (51-6), R501, X501, Ar501, Ar501, L501, m1 and m3 are as defined in the formula (51).
In one embodiment, the compound represented by the formula (51) is represented by any one of the following formulas (51-11) to (51-13):
wherein in the formulas (51-11) to (51-13), R501, X501, Ar501, Ar502, L501, m1, m3 and m4 are as defined in the formula (51).
In one embodiment, the compound represented by the formula (51) is represented by any one of the following formulas (51-21) to (51-25):
wherein in the formulas (51-21) to (51-25), R501, X501, Ar501, Ar502, L501, m1 and m4 are as defined in the formula (51).
In one embodiment, the compound represented by the formula (51) is represented by any one of the following formulas (51-31) to (51-33):
wherein in the formulas (51-31) to (51-33), R501, X501, Ar501, Ar502, L501, m1 to m4 are as defined in the formula (51).
In one embodiment, Ar501 and Ar502 are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, one of Ar501 and Ar502 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and the other is a substituted or unsubstituted monovalent heterocyclic ring having 5 to 50 ring atoms.
As examples of the compound represented by the formula (51), the following compounds can be given, for example. In the following example compounds, Me represents methyl group.
The compound represented by the formula (61) is explained below.
In the formula (61),
at least one pair of R601 and R602, R602 and R603, and R603 and R604 are bonded with each other to form a divalent group represented by the formula (62);
at least one pair of R605 and R606, R606 and R607, and R607 and R608 are bonded with each other to form a divalent group represented by formula (63);
at least one of R601 to R604 that does not form the divalent group represented by the formula (62), and R611 to R614 is a monovalent group represented by the following formula (64);
at least one of R605 to R606 that do not form the divalent gawp represented by the formula (63), and R621 to R624 is a monovalent group represented by the following formula (64);
X601 is an oxygen atom, a sulfur atom, or NR608;
R601 to R608 that do not form the divalent group represented by the formulas (62) and (63) and that is not the monovalent group represented by the formula (64), R611 to R614 and R621 to R624 that are not the monovalent group represented by the formula (64), and R608 are independently
R901 to R907 are as defined in the formula (1);
wherein, in the formula (64), Ar601 and Ar602 are independently
L601 to L603 are independently
In the formula (61), positions at which the divalent represented by the formula (62) and the divalent group represented by the formula (63) are formed are not limited, and said groups can be formed at possible positions in R601 to R606.
In one embodiment, the compound represented by the formula (61) is represented by any one of the following formulas (61-1) to (61-6):
wherein in the formulas (61-1) to (61-6), X601 is as defined in the formula (61);
at least two of R601 to R624 are monovalent groups represented by the formula (64);
R601 to R624 that are not monovalent groups represented by the formula (64) are independently
R901 to R907 are as defined in the formula (1).
In one embodiment, the compound represented by the formula (61) is represented by any one of the following formulas (61-7) to (61-18):
wherein in the formulas (61-7) to (61-18), X601 is as defined in the formula (61); * is a single bond bonding to the monovalent group represented by the formula (64); and R601 to R624 are the same as R601 to R624 that are not monovalent groups represented by the formula (64).
R601 to R608 which do not form the divalent group represented by the formula (62) and (63) and are not monovalent groups represented by the formula (64), and R611 to R614 and R621 to R624 which are not monovalent groups represented by the formula (64) are preferably independently
The monovalent group represented by the formula (64) is preferably represented by the following formulas (65) or (66)
wherein in the formula (65), R631 to R640 are independently
R901 to R907 are as defined in the formula (1).
In the formula (66), Ar601, L601 and L603 are as defined in the formula (64); and HAr601 is a structure represented by the following formula (67);
wherein in the formula (67) X602 is an oxygen atom or a sulfur atom;
any one of R641 to R648 is a single bond bonding to L603;
R641 to R648 which are not single bonds are independently
R901 to R907 are as defined in the formula (1).)
As specific example of the compound represented by the formula (61), in addition to the compounds described in WO2014/104144, the following compounds can be given, for example. In the following example compounds, Me represents methyl group.
The compound represented by the formula (71) is explained below.
In the formula (71),
A701 ring and A701 ring are independently
one or more rings selected from the group consisting of A701 ring and A702 ring are bonded to the bond * of the structure represented by the following formula (72);
wherein, in the formula (72),
A703 rings are independently
X701 is NR703, C(R704)(R705), Si(R706(R707), Ge(R708)(R709), O, S or Se;
R701 and R702 are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring or do not form a substituted or unsubstituted saturated or unsaturated ring;
R701 and R702 that do not form the substituted or unsubstituted, saturated or unsaturated ring, and R703 to R709 are independently
R901 to R907 are as defined in the formula (1).
One or more selected from the group consisting of A701 ring and A702 ring is bonded to * in the structure represented by the formula (72). That is, in one embodiment, the ring carbon atom of the aromatic hydrocarbon ring or the ring atom of the heterocyclic ring of A701 ring is bonded to * in the structure represented by the formula (72). In one embodiment, the ring carbon atom of the aromatic hydrocarbon ring or the ring atom of the heterocyclic ring of A702 ring is bonded to * in the structure represented by the formula (72).
In one embodiment, the group represented by the following formula (73) is bonded to one or both of A701 ring and A702 ring.
In the formula (73), Ar701 and Ar702 are independently
L701 to L703 are independently
In one embodiment, in addition to A701 ring, the ring carbon atom of the aromatic hydrocarbon ring or the ring atom of the heterocyclic ring of A701 ring is bonded to * in the structure represented by the formula (72). In this case, the structures represented by formula (72) may be the same or different.
In one embodiment, R701 and R702 are independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, R701 at R702 are bonded with each other to form a fluorine structure.
In one embodiment, Ar701 ring and Ar702 ring are substituted or unsubstituted aromatic hydrocarbon rings having 6 to 50 ring carbon atoms, and they are substituted or unsubstituted benzene rings, for example.
In one embodiment, Ar703 ring is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, and it is a substituted or unsubstituted benzene ring, for example.
In one embodiment, X701 is O or S.
As specific example of the compound represented by the formula (71), the following compounds can be given, for example. In the following example compounds, Me represents methyl group.
The compound represented by the formula (81) is explained below.
In the formula (81),
A801 ring is a ring represented by the formula (82) which is fused to an adjacent ring at an arbitrary position;
A802 ring is a ring represented by the formula (83) which is fused to an adjacent ring at an arbitrary position;
two bonds * bond to A803 ring at an arbitrary position;
X801 and X802 are independently C(R803)(R804), Si(R805)(R806), an oxygen atom, or a sulfur atom;
A803 ring is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms;
Ar801 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring atoms;
R801 to R806 are independently
R901 to R907 are as defined in the formula (1);
m801 and m802 are independently an integer of 0 to 2; when m801 is 2, R801's may be the same as or different from each other, and when m802 is 2, R802's may be the same as or different from each other;
a801 is an integer of 0 to 2; when a801 is 0 or 1, the structure in the parentheses indicated by “3-a801” may be the same or different from each other, when a801 is 2, Ar801s may be tie same or different from each other.
In one embodiment, Ar801 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
In one embodiment, A803 ring is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 ring carbon atoms, and it is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted anthracene ring, for example.
In one embodiment, R803 and R804 are independently a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
In one embodiment, a801 is 1.
As specific example of the compound represented by the formula (81), the following compounds can be given, for example.
Specific examples of the above groups are as described in [Definition] of this specification.
In the organic EL device according to one aspect of the invention, known materials and device configurations may be applied as long as the device contains a cathode, an anode, and an emitting layer deposed between the cathode and the anode, and the emitting layer contains a compound represented by the following formula (1) and one or more compounds selected from the group consisting of a compound represented by formula (11), a compound represented by formula (21), a compound represented by formula (31), a compound represented by formula (41), a compound represented by formula (51), a compound represented by formula (61), a compound represented by formula (71) and a compound represented by formula (81) as described above, and as long as the effect of the invention is not impaired.
In one embodiment, the emitting layer contains the compound represented by the formula (1A) and the compound represented by the formula (43D).
In one embodiment, the compound represented by the formula (1A) is one or more selected from the group consisting of the compounds represented by the following formulas BH-1, BH-2, BH-4, BH-5 and BH-9; and
the compound represented by the formula (43D) is one or more selected from the group consisting of the compounds represented by the following formulas BD-9, BD-10, BD-11, and BD-12.
Hereinbelow, an explanation will be made on elements and materials other than the above-mentioned compound constituting each layer that can be used in the organic EL device according to one aspect of the invention.
The substrate is used as a supporting body of the emitting device. As the substrate, glass, quarts, plastic or the like can be used. Further, a flexible substrate may be used. The flexible substrate means a substrate that can be bent. For example, a plastic substrate made of polycarbonate or vinyl polychloride or the like can be given.
In an anode formed on a substrate, it is preferable to use a metal having a large work function (specifically, 4.0 eV or more), an alloy, an electric conductive compound, a mixture of these or the like. Specifically, indium oxide-tin oxide (ITO: Indium Tin Oxide), Indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, indium oxide containing zinc oxide, graphene, or the like can be given. In addition, gold (Au), platinum (Pt) or a nitride of a metal material (e.g. titanium nitride) or the like can be given.
The hole-injecting layer is a layer containing a substance having a high hole-injecting property. As a substance having a high hole-injecting property, a substance selected from molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, an aromatic amine compound, a polymer compound (oligomer, dendrimer, polymer, etc.) or the like can also be used
The hole-transporting layer is a layer containing a substance having a high hole-transporting property. For the hole-transporting layer, aromatic amine compounds, carbazole derivatives, anthracene derivatives and the like can be used. Polymer compounds such as poly (N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used. However, any substance other than these may be used as long as it is a substance having a higher transporting property for holes than electrons. Note that the layer containing a substance having a high hole-transporting property is not limited to a single layer, but may be a stacked body of two or more layers made of the above substances.
The emitting layer is a layer that comprises a substance having high luminous property, and various materials can be used. For example, as the substance having high luminous property, a fluorescent compound that emits fluorescent light or a phosphorescent compound that emits phosphorescent light can be used. The fluorescent compound is a compound capable of emitting light from a singlet excited state and the phosphorescent compound is a compound capable of emitting light from a triplet excited state.
As a blue fluorescent material that can be used for the emitting layer, pyrene derivatives, styrylamine derivatives, chrysene derivatives, fluoranthene derivatives, fluorene derivatives, diamine derivatives, triarylamine derivatives and the like can be used. An aromatic amine derivative or the like can be used as a green fluorescent light-emitting material that can be used in the emitting layer. As a red fluorescent material which can be used in emitting layer, a tetracene derivative, a diamine derivative or the like can be used.
Metal complexes such as iridium complexes, osmium complexes, platinum complexes and the like are used as the blue phosphorescent material that can be used in the emitting layer. An iridium complex or the like is used as a green phosphorescent material that can be used in the emitting layer. Metal complexes such as iridium complexes, platinum complexes, terbium complexes, europium complexes and the like are used as red phosphorescent materials that can be used in the emitting layer.
The emitting layer may have a structure in which the substance having high luminescent property (guest material) described above is dispersed in another substance (host material). In addition to the compound represented by the formula (1), various materials can be used as substances for dispersing substances with high luminescent properties, and is preferable to use a material having a high lowest unoccupied molecular orbital level (LUMO level) and a low highest occupied molecular orbital level (HOMO level), rather than a material having a high luminous property.
As a substance (host material) for dispersing a substance having a high luminous property, 1) a metal complex such as an aluminum complex, a beryllium complex or a zinc complex, 2) a heterocyclic compound such as an oxadiazole derivative, a benzimidazole derivative, a phenanthroline derivative or the like, 3) a fused aromatic compound such as a carbazole derivative, an anthracene derivative, a phenanthrene derivative, a pyrene derivative or a chrysene derivative, and 4) an aromatic amine compound such as a triarylamine derivative or a fused polycyclic aromatic amine derivative are used.
The electron-transporting layer is a layer containing a substance having a high electron-transporting property. For the electron-transporting layer, 1) a metal complex such as an aluminum complex, a beryllium complex, or a zinc complex, 2) a heteroaromatic compound such as an imidazole derivative, a benzimidazole derivative, an azine derivative, a carbazole derivative or a phenanthroline derivative, and 3) a polymer compound can be used.
The electron-injection layer is a layer containing a substance having a high electron-injection property. For the electron-injection layer, alkali metals, alkaline earth metals or a compound thereof such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), lithium oxide (LiOx) or the like can be used.
It is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less) for the cathode. Specific examples of such cathode material include elements belonging to Group 1 or Group 2 of the periodic table of elements, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), an alloy containing these metals (for example, MgAg and AlLi), a rare earth metal such as europium (Eu) and ytterbium (Yb), and an alloy containing a rare earth metal.
In the organic EL device according to one aspect of the invention, the method for forming each layer is not particularly restricted. A conventionally known forming method such as a vacuum deposition method, a spin coating method or the like can be used. Each layer such as the emitting layer or the like can be formed by a vacuum deposition method, a molecular beam evaporation method (MBE method), or a known coating method such as a dipping method, a solution spin coating method, a casting method, a bar coating method, or the like, that uses a solution of a material forming each layer dissolved in a solvent.
In the organic EL device according to one aspect of the invention, the thickness of each layer is not particularly restricted. In general, in order to suppress occurrence of defects such as pinholes and to suppress the applied voltage and to improve luminous efficiency, the thickness is normally preferably in a range of several nm to 1 μm.
The electronic device according to one aspect of the invention is characterized in that it is provided with the organic EL device according to one aspect of the invention.
Specific examples of the electronic device include a display element such as an organic EL panel module; a display such as a TV, a mobile phone or a PC; and emitting devices such as lightings and lights for automobiles or the like.
Now, the invention explained in detail with reference to Examples and Comparative Examples. However, it should be understood that the invention be not restricted at all by these Examples.
Synthesis scheme of BH-1 is shown below. Hereinafter, TfO represents trifluoromethanesulfonate.
Under an argon atmosphere, a mixture of 40.0 g of anthracene d-10, 38.0 g of NBS (N-bromosuccinimide), and 1200 mL of dimethyl formamide (DMF) was stirred at room temperature for 16 hours. The resultant reaction liquid was cooled to room temperature, followed by filtration. Then, the solvent of the obtained filtrate was distilled off under reduced pressure. The obtained residue was purified by column chromatography to give 42.0 g of BH-1-1 in an yield of 75%.
Under an argon atmosphere, a mixture of 42.0 g of BH-1-1, 30.0 g of 1-naphthaleneboronic acid, 3.70 g of tetrakistriphenylphosphine palladium, 160 mL of a 2M sodium carbonate aqueous solution, and 750 mL of dimethoxyethane (DME) was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel chromatography to give 29.6 g of BH-1-2 in an yield of 65%.
Under an argon atmosphere, a mixture of 260 g of BH-1-2, 15.9 g of NBS, and 500 mL of DMF is stirred at 80° C. for 12 hours. The resultant reaction liquid was cooled to room temperature, followed by filtration. Then, the solvent of the obtained filtrate was distilled off under reduced pressure. The obtained residue was purified by column chromatography to give 16.4 g of BH-1-3 in en yield of 47%.
Under an argon atmosphere, a reactor was charged with 13.0 g of BH-1-3 and 130 mL of tetrahydrofuran (THF), and cooled to −78° C. To the reactor, 25 mL of a 1.6M n-butyllithium in hexane was added, and the reaction mixture was stirred for one hour. Subsequently, 19 g of triisopropoxyboron was added thereto, followed by stirring for more one hour. The reaction liquid was warmed to room temperature, stirred for one hour. Then, 480 mL of a 1N hydrochloric acid solution was added thereto, followed by stirring for 30 minutes. The organic phase of the resultant reaction liquid was extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 8.4 g of BH-1-4 in an yield of 71%.
Under an argon atmosphere, a mixture of 3.1 g of BH-1-4, 2.5 g of BH-1-5, 0.200 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 60 mL of DME was stirred at 80° C. for 8 hours. Then, the resultant reaction liquid was cooled to room temperature, extracted with ethyl acetate. The organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystallization to give 2.5 g of BH-1 in an yield of 56%.
The compound was identified by molecular weight determination with FD/MS (Field Desorption Mass Spectrometry). It was confirmed that m/e=514 for the molecular weight of 514.
Synthesis scheme of BH-2 is shown below.
Under an argon atmosphere, a mixture of 4.0 g of BH-1-4, 3.5 g of BH-2-1, 0.260 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recyclization to give 2.9 g of BH-2 in an yield of 59%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=438 for the molecular weight of 438.
Synthesis scheme of BH-3 is shown below.
Under an argon atmosphere, a mixture of 4.0 g of BH-1-4, 4.5 g of BH-3-1, 0.260 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was wasted with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced plasma. The obtained residue was purified by silica gel column chromatography and recrystallization to give 3.2 g of BH-3 in an yield of 55%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=514 for the molecular weight of 514.
Synthesis scheme of BH-4 is shown below.
Under an argon atmosphere, a mixture of 42.0 g of BH-1-1, 21.3 g of phenylboronic acid, 3.70 g of tetrakisbiphenylphosphine palladium, 160 mL of a 2M sodium carbonate aqueous solution, and 750 mL of dimethoxyethane (DME) was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 29.9 g of BH-4-1 in an yield of 72%.
Under an argon atmosphere, a mixture of 23.5 g of BH-4-1, 15.9 g of NBS, and 500 mL of DMF was stirred at 80° C. for 12 hours. The resultant reaction liquid was cooled to room temperature, and filtered. Subsequently, the solvent of the obtained filtrate was distilled off under reduced pressure. The obtained residue was purified by column chromatography to give 15.2 g of BH-4-2 in an yield of 50%.
Under an argon atmosphere, a reactor was charged with 11.0 g of BH-4-2, aid 130 mL of tetrahydrofuran (THF), and cooled to −78° C. To the reactor 25 mL of a 1.6M n-butyllithium in hexane was added, and the reaction mixture was stirred for one hour. Then, 19 g of triisopropoxy boron was added thereto, and stirred for one hour. The reaction liquid was warmed to room temperature, stirred for one hour. Subsequently, 480 mL of a 1N hydrochloric acid solution was added thereto and stirred for 30 minutes. The organic phase of the resultant reaction liquid was extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 7.4 g of BH-4-3 in an yield of 75%.
Under an argon atmosphere, a mixture of 2.7 g of BH-4-3, 25 g of BH-4-4, 0.200 g of tetakistriphenylphosphine palladium, 10 ml of a 2M sodium carbonate aqueous solution, and 60 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystallization to give 1.8 g of BH-4 in an yield of 45%.
The compound was identified by molecular weight determination with FD/MS (Field Desorption Mass Spectrometry). It was confirmed that m/e=464 for the molecular weight of 464.
Synthesis scheme of BH-5 is shown below.
Under an argon atmosphere, a mixture of 3.4 g of BH-4-3, 4.5 g of BH-5-1, 0.260 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Subsequently, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by slice gel column chromatography and recrystallization to give 22 g of BH-5 in an yield of 43%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=464 for the molecular weight of 464.
Synthesis scheme of BH-6 is shown below.
Under an argon atmosphere, a mixture of 3.4 g of BH-4-3, 4.5 g of BH-6-1, 0.260 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystallization to give 2.5 g of BH-6 in an yield of 47%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=464 for the molecular weight of 464.
Synthesis scheme of BH-7 is shown below.
Under an argon atmosphere, a mixture of 39.9 g of BH-1-1, 29.7 g of 1-naphthalene boronic acid d-7, 3.51 g of tetrakistriphenylphosphine palladium, 160 mL of a 2M sodium carbonate aqueous solution, and 750 mL of dimethoxyethane (DME) was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 32.2 g of BH-7-1 in an yield of 67%.
Under an argon atmosphere, a mixture of 32.0 g of BH-7-1, 17.8 g of NBS, and 560 mL of DMF was stirred at 80° C. for 12 hours. The resultant reaction liquid was cooled to room temperature, and filtered. Then, the solvent of the obtained filtrate was distilled off under reduced pressure. The obtained residue was purified by column chromatography to give 17.9 g of BH-7-2 in an yield of 45%.
Under an argon atmosphere, a reactor was charged with 12.0 g of BH-7-2, and 120 mL of tetrahydrofuran (THF), and cooled to −78° C. To the reactor, 23.2 mL of a solution of 1.6M n-butyllithium in hexane was added, and stirred for one hour. Then, 18 g of triisopropoxyboron was added to the reaction liquid, and stirred for more one hour. The reaction liquid was warmed to room temperature, and stirred for one hour. Subsequently, 450 mL of a 1N hydrochloric acid solution was added thereto, and the reaction liquid was stirred for 30 minutes. The organic phase of the resultant reaction liquid was extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 7.2 g of BH-7-3 in an yield of 66%.
Under an argon atmosphere, a mixture of 3.6 g of BH-7-3, 2.9 g of BH-7-4, 0.230 g of tetrakistriphenylphosphine palladium, 11.5 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystallization to give 2.1 g of BH-7 in an yield of 40%.
The compound was identified by molecular weight determination with FD/MS (Field Desorption Mass Spectrometry). It was confirmed that m/e>532 for the molecular weight of 532.
Synthesis scheme of BH-8 is shown below.
Under an argon atmosphere, a mixture of 3.6 g of BH-7-3, 2.6 g of 2-bromonaphthalene d-7, 0.260 g of tetrakisbiphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 70 mL of DME was stirred at 80° C. for 8 hours. The resultant reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystalization to give 2.1 g of BH-8 in an yield of 47%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=452 for the molecular weight of 452.
Synthesis scheme of BH-9 is shown below.
Under an argon atmosphere, a mixture of 3.1 g of BH-4-3, 4.1 g of BH-9-1, 0.234 g of tetrakistriphenylphosphine palladium, 10 mL of a 2M sodium carbonate aqueous solution, and 60 mL of DME was stirred at 80° C. for 9 hours. The resilient reaction liquid was cooled to room temperature, and extracted with ethyl acetate. Then, the organic phase was washed with water, and dried over anhydrous magnesium sulfate, followed by distillation of the solvent under reduced pressure. The obtained residue was purified by silica gel column chromatography and recrystallization to give 2.8 g of BH-9 in an yield of 54%. The compound was identified by molecular weight determination with FD/MS. It was confirmed that m/e=464 for the molecular weight 464.
Compounds used in the following Examples and Comparative Examples are shown below.
A glass substrate of 25 mm by 75 mm by 1.1 mm thick with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning with isopropyl alcohol for 5 minutes, and then subjected to UV-ozone cleaning for 30 minutes. The thickness of the ITO was 130 nm.
The cleaned glass substrate with a transparent electrode was mounted in a substrate holder of a vacuum vapor deposition apparatus. First, the compound HI-1 was deposited on the surface where the transparent electrode was formed so as to cover the transparent electrode, thereby a 5 nm-thick HI-1 film was formed. This HI-1 film serves as a hole-injecting layer.
Subsequent to the formation of the HI-1 film, the compound HT-1 was deposited, whereby a 80 nm-thick HT-1 film was formed on the HI-1 film. This HT-1 film serves as a hole-transporting layer (first hole-transporting layer).
Subsequent to the formation of the HT-1 film, the compound HT-2 was deposited, whereby a 10 nm-thick HT-2 film was formed on the HT-1 film. This HT-2 film serves as an electron blocking layer (second hole-transporting layer).
On the HT-2 film, compound BH-1 (host material) and compound BD-1 (dopant material) were co-deposited such that the amount ratio of compound BD-1 became 2 mass %, whereby a 25 nm-thick BH-1:BD-1 film was formed. The BH-1:BD-1 film serves as an emitting layer.
On the emitting layer, compound ET-1 was deposited, whereby a 10 nm-thick ET-1 film was formed. This ET-1 film serves as a hole barrier layer.
On the ET-1 film, compound ET-2 was deposited, whereby a 15 nm-thick ET-2 film was formed. This ET-2 film serves as an electron transporting layer. On this ET-2 film, LiF was deposited, whereby a 1 nm-thick LiF film was formed. On this LiF film, metal Al was deposited, whereby a 80 nm-thick metal cathode was formed. By the above-mentioned procedures, an organic EL device was fabricated.
The resultant organic EL device has the blowing layer structure: ITO(130)/HI-1(5)/HT-1(80)/HT-2(10)/BH-1:BD-1(25: 2 mass %)/ET-1(10)/ET-2(15)/LiF(1)/AI(80).
The numerical value in the parenthesis indicates the film thickness (unit nm).
A voltage was applied to the resulting organic EL device such that the current density became 50 mA/cm2, and the time taken until the luminance became 95% of the initial luminance (LT95 (unit hour)) were measured. The results are shown in Table 1.
Further, the CIE1931 chromaticity coordinates (CIEx and CIEy) of the resulting organic EL device at the time when a voltage was applied thereto such that the current density became 10 mA/cm2, were determined from a spectral radiance spectrum measured by means of a spectral radiance meter CS-1000 (manufactured by Konica Minolta, Inc.). The results are shown in Table 1.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 1 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 1.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 2 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 2.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 3 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 3.
Organic EL devices were fabricated it the same manner as in Example 1 except that compounds indicated in Table 4 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 4.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 5 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 5.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 6 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 6.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 7 were used as the materials for the emitting layer, and evaluated. The results are shown in Table 7.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 8 were used as the materials for the emitting layer. The results are shown Table 8.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 9 were used as the materials for the emitting layer. The results are shown in Table 9.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicted in Table 10 were used as the materials for the emitting layer. The results are shown in Table 10.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 11 were used as the materials for the emitting layer. The results are shown in Table 11.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 12 were used as the materials for the emitting layer. The results are shown in Table 12.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 13 were used as the materials for the emitting layer. The results are shown in Table 13.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 14 were used as the materials for the emitting layer. The results are shown in Table 14.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 15 were used as the materials for the emitting layer. The results are shown in Table 15.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 16 were used as the materials for the emitting layer. The results are shown in Table 16.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 17 were used as the materials for the emitting layer. The results are shown in Table 17.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 18 were used as the materials for the emitting layer. The resits are shown in Table 18.
Organic EL devices were fabricated in the sane manner as in Example 1 except that compounds indicated in Table 19 were used as the materials for the emitting layer. The results are shown in Table 19.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 20 were used as the materials for the emitting layer. The results are shown in Table 20.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 21 ware used as the materials for the writing layer. The results are shown in Table 21.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 22 were used as the materials for the emitting layer. The results are shown in Table 22.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 23 were used as the materials for the emitting layer. The results are shown in Table 23.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 24 were used as the materials for the emitting layer. The results are shown in Table 24.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 25 were used as the materials for the emitting layer. The results are shown in Table 25.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 26 were used as the materials for the emitting layer. The results are shown in Table 26.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 27 were used as the materials for the emitting layer. The results are shown in Table 27.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds in Table 28 were used as the materials for the emitting layer. The results are shown in Table 28.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 29 were used as the materials for the emitting layer. The results are shown in Table 29.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 30 were used as the materials for the emitting layer. The results are shown in Table 30.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 31 were used as the materials for the emitting layer. The results are shown in Table 31.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 32 were used as the materials for the emitting layer. The resits are shown in Table 32.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 33 were used as the materials for the emitting layer. The results are shown in Table 33.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 34 were used as the materials for the emitting layer. The rests are shown in Table 34.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 35 were used as the materials for the emitting layer. The results are shown in Table 36.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 36 were used as the materials for the emitting layer. The results are shown in Table 36.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 37 were used as the materials for the emitting layer. The results are shown in Table 37.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 38 were used as the materials for the emitting layer. The results are shown in Table 38.
Organ EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 39 were used as the materials for the emitting layer. The results are shown in Table 39.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 40 were used as the materials for the writing layer. The results are shown in Table 40.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 41 were used as the materials for the emitting layer. The results are shown in Table 41.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 42 were used as the materials for the emitting layer. The results are shown in Table 42.
Organic EL devices were fabricated in the same manner as to Example 1 except that compounds indicated in Table 43 were used as the materials for the emitting layer. The results are shown in Table 43.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 44 were used as the materials for the emitting layer. The results are shown in Table 44.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 45 were used as the materials for the emitting layer. The results are shown in Table 45.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 46 were used as the materials for the emitting layer. The results are shown in Table 46.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 47 were used as the materials for the emitting layer. The results are shown in Table 47.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 48 were used as the materials for the emitting layer. The results are shown in Table 48.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 49 were used as the materials for the emitting layer. The results are shown in Table 49.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 50 were used as the materials for the emitting layer. The results are shown in Table 50.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 51 were used as the materials for the emitting layer. The results are shown in Table 51.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 52 were used as the materials for the emitting layer. The results are shown in Table 52.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 53 were used as the materials for the emitting layer. The results are shown in Table 53.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds included in Table 54 were used as the materials for the emitting layer. The results are shown in Table 54.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 55 were used as the materials for the emitting layer. The results are shown in Table 55.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 56 were used as the materials for the emitting layer. The results are shown in Table 56.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 57 were used as the materials for the emitting layer. The results are shown in Table 57.
Organic EL devices were fabricated in the same manner as in Example 1 except that compounds indicated in Table 58 were used as the materials for the emitting layer. The results are shown in Table 58.
From the results shown in Tables 1 to 58, it is understood that the organic EL devices of Examples 1 to 102 in which a particular host material and a particular dopant material were used in combination have a low CIEy value and long lifetime, and simultaneously satisfied both these properties.
Several embodiments and/or examples of the present invention have been described in detail above. However, without substantially departing from novel teachings and effects of the present invention, the person skilled in the art can readily make a number of modifications to the embodiments and/or examples which are exemplifications of these teachings and effects. Thus, these modifications are included in the scope of the present invention.
The documents described in this specification and the contents of the application that serves as the basis of priority claim under Paris convention are incorporated herein by reference in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-188682 | Oct 2018 | JP | national |
| 2019-086182 | Apr 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/039090 | 10/3/2019 | WO | 00 |
