HETEROCYCLIC COMPOUND AND AN ORGANIC ELECTROLUMINESCENCE DEVICE COMPRISING THE HETEROCYCLIC COMPOUND

The present invention relates to specific heterocyclic compounds, a material, preferably an emitter material, for an organic electroluminescence device comprising said specific heterocyclic compounds, an organic electroluminescence device comprising said specific heterocyclic compounds, an electronic equipment comprising said organic electroluminescence device, a light emitting layer comprising at least one host and at least one dopant, wherein the dopant comprises at least one of said specific heterocyclic compounds, and the use of said heterocyclic compounds in an 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.

An organic EL device comprises an emitting layer between the anode and the cathode. Further, there may be a case where it has a stacked layer structure comprising an organic layer such as a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, an electron-transporting layer, etc.

US 2019/214564 A1 relates to boron and nitrogen containing heterocyclic compounds, which can be used as emitters, hosts, charge blocking materials, charge transporting materials, etc. in an electroluminescent device. These novel compounds can offer very narrow emissive spectrum, and obtain high saturated deep blue emission. Also disclosed are an organic light-emitting device and a formulation.

The heterocyclic compounds are characterized by formulae (II), (III) and (IV)

embedded image

wherein Y¹to Y¹⁸are each independently selected from C, CR or N; no fused rings formed by two (adjacent) substituents R are defined.

Specific compounds disclosed in US 2019/214564 A1 are for example:

embedded image

CN106467554 A relates to a boron-containing organic electroluminescent compound, characterized in that the structure of the compound is represented by the general formula (I):

embedded image

In the general formula (I), R₁to R₁₁each independently represent hydrogen, an aryl group, a heteroaryl group, an alkyl group, an alkoxy group, or an arylamine group. No fused rings formed by two (adjacent) residues R₁to R₁₁are defined.

A specific compound disclosed in CN106467554 A is for example:

embedded image

JP2020-123721 A relates to an organic electroluminescent element having a pair of opposed electrodes and a laminated structure of a plurality of layers between the pair of electrodes. The laminated structure includes at least two blue light emitting layers, and at least one of the blue light emitting layers comprises a polycyclic aromatic compound. In a preferred embodiment, the polycyclic aromatic compound is represented by the following formula:

embedded image

wherein

R¹to R¹¹are each independently hydrogen, aryl, heteroaryl, diarylamino, diarylboryl, alkyl, cycloalkyl, alkoxy or aryloxy; it may be optionally substituted, and the adjacent groups of R¹to R³, R⁴to R⁷and R⁸to R¹¹may be bonded together to form an aryl or heteroaryl ring together with a ring, b or c. The ring formed is optionally substituted. X¹and X²each independently is O, N—R, CR₂, S or Se and R is aryl, heteroaryl, cycloalkyl, and, wherein X¹and X²are not simultaneously CR₂, at least one hydrogen in the compound of formula (I) may be substituted with cyano, halogen, or deuterium.

A specific compound disclosed in JP2020-123721 A is for example:

embedded image

CN111471063 A relates to a boron-containing organic compound and application thereof on organic electroluminescent devices, and belongs to the technical field of semiconductors. The structure of the provided compound is shown as a general formula (I).

embedded image

CN111574543 A relates to a boron-containing organic compound and application thereof to an organic light-emitting device, belonging to the technical field of semiconductors. The structure of the boron-containing organic compound is shown as a general formula (I).

embedded image

However, the specific structure and substitution pattern of polycyclic compounds has a significant impact on the performance of the polycyclic compounds in organic electronic devices.

Notwithstanding the developments described above, there remains a need for organic electroluminescence devices comprising new materials, especially dopant (=emitter) materials, to provide improved performance of electroluminescence devices.

Accordingly, it is an object of the present invention, with respect to the aforementioned related art, to provide materials suitable for providing organic electroluminescence devices which ensure good performance of the organic electroluminescence devices, especially good EQEs and/or a long lifetime. More particularly, it should be possible to provide dopant (=emitter) materials, especially blue light emitting dopant materials having a narrow spectrum (smaller FWHM), i.e. good color purity when used as dopant in organic electroluminescence devices.

Said object is according to the present invention solved by a heterocyclic compound represented by formula (I):

embedded image

wherein

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸each independently represents hydrogen; deuterium; an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; an alkylhalide group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted; CN; N(R²²)₂; OR²⁰; SR²⁰; B(R²¹)₂; SiR²⁴R²⁵R²⁶or halogen;

R⁵and R⁶together may form a ring structure which is unsubstituted or substituted;

and

at least two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸together form a ring structure which is unsubstituted or substituted,

R¹and R¹⁸do not form together a ring structure;

and

(R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring,

R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;

and/or

R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸forms a ring structure which is unsubstituted or substituted; and

R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²⁴and R²⁵together form a ring structure which is unsubstituted or substituted.

The compounds of formula (I) can be in principal used in any layer of an EL device. Preferably, the compound of formula (I) is a dopant (=emitter) in organic EL elements, especially in the light-emitting layer, more preferably a fluorescent dopant. Particularly, the compounds of formula (I) are used as fluorescent dopants in organic EL devices, especially in the light-emitting layer.

The term organic EL device (organic electroluminescence device) is used interchangeably with the term organic light-emitting diode (OLED) in the present application.

It has been found that the specific compounds of formula (I) show a narrow emission characteristic, preferably a narrow fluorescence, more preferably a narrow blue fluorescence. Such a narrow emission characteristic is suitable to prevent energy losses by outcoupling. The compounds of formula (I) according to the present invention preferably have a Full width at half maximum (FWHM) of lower than 50 nm, more preferably lower than 40 nm, most preferably lower than 35 nm, further most preferably lower than 30 nm, even further most preferably lower than 26 nm.

It has further been found that organic EL devices comprising the compounds of the present invention are generally characterized by high external quantum efficiencies (EQE) and/or long lifetimes, especially when the specific compounds of formula (I) are used as dopants (light emitting material), especially fluorescent dopants in organic electroluminescence devices.

Examples of the optional substituent(s) indicated by “substituted or unsubstituted” and “may be substituted” referred to above or hereinafter include an aryl group having from 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms which is in turn unsubstituted or substituted, a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is in turn unsubstituted or substituted, an alkyl group having 1 to 20, preferably 1 to 8 carbon atoms, a cycloalkyl group having 3 to 20, preferably 3 to 10 carbon atoms, a group OR²⁰, an alkylhalide group having 1 to 20, preferably 1 to 8 carbon atoms, a group N(R²²)₂, a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a carboxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, a carboxamidalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, a silyl group SiR²⁴R²⁵R²⁶, B(R²¹)₂, a group SR²⁰, a carboxyaryl group having 6 to 18 ring carbon atoms in the aryl residue and a carboxamidaryl group having 6 to 18 ring carbon atoms in the aryl residue;

or

two adjacent substituents together form a ring structure which is in turn unsubstituted or substituted;

R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to N, O, S or B; an alkyl group having from 1 to 20 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20 ring carbon atoms which is unsubstituted or substituted; and/or two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;

or

R²⁰, R²¹, and/or R²²together with an adjacent substituent form a ring structure which is unsubstituted or substituted;

R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²⁴and R²⁵together form a ring structure which is unsubstituted or substituted.

The terms hydrogen, halogen, an alkyl group having from 1 to 20 carbon atoms which is unsubstituted or substituted, an alkylhalide group having from 1 to 20 carbon atoms which is unsubstituted or substituted, a cycloalkyl group having from 3 to 20 ring carbon atoms which is unsubstituted or substituted, a substituted or unsubstituted aryl group having 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms; a substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, a carboxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, a carboxamidalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, a carboxyaryl group having 6 to 18 ring carbon atoms in the aryl residue, a carboxamidaryl group having 6 to 18 ring carbon atoms in the aryl residue, N(R²²)₂, OR²⁰, SR²⁰, SR²⁰, SiR²⁴R²⁵R²⁶and B(R²¹)₂, are known in the art and generally have the following meaning, if said groups are not further specified in specific embodiments mentioned below:

If deuterium is not explicitly listed in the invention, hydrogen includes isomers differing in the number of neutrons, i.e. protium, deuterium and tritium.

The substituted or unsubstituted aryl group having 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms most preferably having from 6 to 13 ring carbon atoms, may be a non-condensed aryl group or a condensed aryl group. Specific examples thereof include phenyl group, naphthyl group, phenanthryl group, biphenyl group, terphenyl group, fluoranthenyl group, triphenylenyl group, phenanthrenyl group, fluorenyl group, indenyl group, anthracenyl, chrysenyl, spirofluorenyl group, benzo[c]phenanthrenyl group, with phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, triphenylenyl group, fluorenyl group, indenyl group and fluoranthenyl group being preferred, phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, phenanthrene-9-yl group, phenanthrene-3-yl group, phenanthrene-2-yl group, triphenylene-2-yl group, fluorene-2-yl group, especially a 9,9-di-C_1-20alkylfluorene-2-yl group, like a 9,9-dimethylfluorene-2-yl group, a 9,9-di-C_6-18arylfluorene-2-yl group, like a 9,9-diphenylfluorene-2-yl group, or a 9,9-di-C_5-18heteroarylfluorene-2-yl group, 1,1-dimethylindenyl group, fluoranthene-3-yl group, fluoranthene-2-yl group and fluoranthene-8-yl group being more preferred, and phenyl group being most preferred.

The substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, most preferably having from 5 to 13 ring atoms, may be a non-condensed heteroaryl group or a condensed heteroaryl group. Specific examples thereof include the residues of pyrrole ring, isoindole ring, benzofuran ring, isobenzofuran ring, benzothiophene, dibenzothiophene ring, isoquinoline ring, quinoxaline ring, quinazoline, phenanthridine ring, phenanthroline ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, acridine ring, carbazole ring, furan ring, thiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, dibenzofuran ring, triazine ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, triazole ring, imidazole ring, indolidine ring, imidazopyridine ring, 4-imidazo[1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a]benzimidazoyl, and benzimidazolo[2,1-b][1,3]benzothiazolyl, with the residues of benzofuran ring, indole ring, benzothiophene ring, dibenzofuran ring, carbazole ring, and dibenzothiophene ring being preferred, and the residues of benzofuran ring, 1-phenylindol ring, benzothiophene ring, dibenzofuran-1-yl group, dibenzofuran-3-yl group, dibenzofuran-2-yl group, dibenzofuran-4-yl group, 9-phenylcarbazole-3-yl group, 9-phenylcarbazole-2-yl group, 9-phenylcarbazole-4-yl group, dibenzothiophene-2-yl group, and dibenzothiophene-4-yl, dibenzothiophene-1-yl group, and dibenzothiophene-3-yl group being more preferred.

Examples of the alkyl group having from 1 to 20 carbon atoms which is unsubstituted or substituted include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, with methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group being preferred. Preferred are alkyl groups having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Suitable examples for alkyl groups having 1 to 8 carbon atoms respectively 1 to 4 carbon atoms are mentioned before. Further examples of substituted alkyl groups are aralkyl groups, i.e. CH₂-aryl groups, wherein suitable aryl groups are mentioned above. Preferred aralkyl groups are benzyl groups.

Examples of the alkylhalide group having from 1 to 20 carbon atoms which is unsubstituted or substituted include those disclosed as alkyl groups wherein the hydrogen atoms thereof are partly or entirely substituted by halogen atoms. Preferred alkylhalide groups are fluoroalkyl groups having 1 to 20 carbon atoms including the alkyl groups mentioned above wherein the hydrogen atoms thereof are partly or entirely substituted by fluorine atoms, for example CF₃.

Examples of the cycloalkyl group having from 3 to 20 ring carbon atoms which is unsubstituted or substituted include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and adamantyl group, with cyclopentyl group, and cyclohexyl group being preferred. Preferred are cycloalkyl groups having 3 to 10 carbon atoms. Suitable examples for cycloalkyl groups having 3 to 10 carbon atoms are mentioned before.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine being preferred.

The group OR²⁰is preferably a C_1-20alkoxy group or a C_6-18aryloxy group. Examples of an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups mentioned above. Examples of an aryloxy group having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups mentioned above, for example —OPh.

The group SR²⁰is preferably a C_1-20alkylthio group or a C_6-18arylthio group. Examples of an alkylthio group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups mentioned above. Examples of an arylthio group having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups mentioned above, for example —SPh.

The group N(R²²)₂is preferably an C_1-20alkyl and/or C_6-18aryl and/or heteroaryl (having 5 to 18 ring atoms) substituted amino group. Examples of an alkylamino group (alkyl substituted amino group) having 1 to 20 ring carbon atoms include those having an alkyl portion selected from the alkyl groups mentioned above. Examples of an arylamino group (aryl substituted amino group) having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups mentioned above, for example —NPh₂. Examples of a heteroarylamino group (heteroaryl substituted amino group), preferably a heteroarylamino group having 5 to 18 ring atoms include those having an aryl portion selected from the heteroaryl groups mentioned above.

The group B(R²¹)₂is preferably an C_1-20alkyl and/or C_6-18aryl and/or heteroaryl (having 5 to 18 ring atoms) substituted boron group. Examples of an alkylboron group (alkyl substituted boron group) having 1 to 20 ring carbon atoms include those having an alkyl portion selected from the alkyl groups mentioned above. Examples of an arylboron group (aryl substituted boron group) having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups mentioned above. Examples of a heteroarylboron group (heteroaryl substituted boron group), preferably a heteroarylboron group having 5 to 18 ring atoms include those having an aryl portion selected from the heteroaryl groups mentioned above.

The group SiR²⁴R²⁵R²⁶is preferably a C_1-20alkyl and/or C_6-18aryl substituted silyl group. Preferred examples of C_1-20alkyl and/or C_6-18aryl substituted silyl groups include alkylsilyl groups having 1 to 8 carbon atoms in each alkyl residue, preferably 1 to 4 carbon atoms, including trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, dimethyltertiarybutylsilyl group, diethylisopropylsilyl group, and arylsilyl groups having 6 to 18 ring carbon atoms in each aryl residue, preferably triphenylsilyl group, and alkyl/arylsilyl groups, preferably phenyldimethylsilyl group, diphenylmethylsilyl group, and diphenyltertiarybutylsilyl group, with diphenyltertiarybutylsilyl group and t-butyldimethylsilyl group being preferred.

More preferably, in the heterocyclic compounds of formula (I), the ring formed by joining (R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) together does not comprise a silyl group.

Examples of a carboxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, those having an alkyl portion selected from the alkyl groups mentioned above.

Examples of a carboxyaryl group having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms, include those having an aryl portion selected from the aryl groups mentioned above.

Examples of a carboxamidalkyl group (alkyl substituted amide group) having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms include those having an alkyl portion selected from the alkyl groups mentioned above.

Examples of a carboxamidaryl group (aryl substituted amide group) having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms, include those having an aryl portion selected from the aryl groups mentioned above.

The optional substituents preferably each independently represents an aryl group having from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having 1 to 8 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having 3 to 10 carbon atoms which is unsubstituted or substituted; CN; N(R²²)₂; SR²⁰; OR²⁰; SiR²⁴R²⁵R²⁶, F or CF₃;

or

two adjacent substituents together form a ring structure which is in turn unsubstituted or substituted;

R²⁰and R²²each independently represents an aryl group having from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to N or O or S; an alkyl group having 1 to 8 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 10 ring carbon atoms which is unsubstituted or substituted;

or

R²⁰and/or R²²together with an adjacent substituent form a ring structure which is in turn unsubstituted or substituted;

R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²⁴and R²⁵together form a ring structure which is unsubstituted or substituted.

More preferably, the optional substituents each independently represents an aryl group having from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 10 ring carbon atoms which is unsubstituted or substituted; CN; N(R²²)₂or F;

or

two adjacent substituents together form a ring structure which is in turn unsubstituted or substituted;

R²²represents an aryl group having from 6 to 18 ring carbon atoms which is unsubstituted or substituted; or an alkyl group having from 1 to 4 carbon atoms which is unsubstituted or substituted:

or

R²²together with an adjacent substituent forms a ring structure which is in turn unsubstituted or substituted.

Most preferably, the optional substituents each independently represents an alkyl group having 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 10 ring carbon atoms which is unsubstituted or substituted; an aryl group having 6 to 13 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 13 ring atoms which is unsubstituted or substituted; CN; or N(R²²)₂;

The optional substituents mentioned above may be further substituted by one or more of the optional substituents mentioned above.

The number of the optional substituents depends on the group which is substituted by said substituent(s). The maximum number of possible substituents is defined by the number of hydrogen atoms present. Preferred are 1, 2, 3, 5, 6, 7, 8 or 9 optional substituents per group which is substituted, more preferred are 1, 2, 3, 5, 5, 6 or 7 optional substituents, most preferred are 1, 2, 3, 4 or 5 optional substituents, further most preferred are 1, 2, 3, 4 or 5 optional substituents, even further most preferred are 1, 2, 3 or 4 optional substituents and even more further most preferred are 1 or 2 optional substituents per group which is substituted. In a further preferred embodiment, some or all of the groups mentioned above are unsubstituted.

In a further preferred embodiment, the total number of substituents in the compound of formula (I) is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, 4, 5, or 6, i.e. the remaining residues are hydrogen.

The “carbon number of a to b” in the expression of “substituted or unsubstituted X group having a to b carbon atoms” is the carbon number of the unsubstituted X group and does not include the carbon atom(s) of an optional substituent.

The term “unsubstituted” referred to by “unsubstituted or substituted” means that a hydrogen atom is not substituted by one the groups mentioned above.

An index of 0 in the definition in any formula mentioned above and below means that a hydrogen atom is present at the position defined by said index.

The compounds of formula (I)

In the heterocyclic compounds represented by formula (I)

embedded image

The residues have the following meanings:

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸each independently represents hydrogen; deuterium; an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; an alkylhalide group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted; CN; N(R²²)₂; OR²⁰; SR²⁰; B(R²¹)₂; SiR²⁴R²⁵R²⁶or halogen;

R⁵and R⁶together may form a ring structure which is unsubstituted or substituted;

and

at least two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸together form a ring structure which is unsubstituted or substituted,

R¹and R¹⁸do not form together a ring structure;

and

(R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring,

R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;

and/or

R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸forms a ring structure which is unsubstituted or substituted; and

R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²⁴and R²⁵together form a ring structure which is unsubstituted or substituted.

Examples for ring structures formed by two adjacent residues are shown below (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

X″ and Y″ each independently represents O, CR^aR^b, S, BR^cor NR^c, R^a, R^b, R^cand R^deach independently represents H, C₁to C₈alkyl or substituted or unsubstituted C₆to C₁₈aryl, preferably C₁to C₄alkyl or substituted or unsubstituted C₆to C₁₀aryl, more preferably methyl or unsubstituted or substituted phenyl,

E₁, F₁, F₂, G₁, H₁, I₁, I₂, K₁, L₁, M₁and N₁each independently represents a substituted or unsubstituted aryl group having 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms,

and

the dotted lines are bonding sites.

In a further embodiment, E₁represents a substituted or unsubstituted cycloalkyl group having 5 to 60, preferably from 5 to 30, more preferably from 5 to 18 ring carbon atoms, e.g. one of the following ring structures is formed by two adjacent residues:

embedded image

wherein

X is defined above,

and

the dotted lines are bonding sites.

Preferred ring structures formed by two adjacent residues are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

R^a, R^b, R^cand R^deach independently represents H, C₁to C₈alkyl or substituted or unsubstituted C₆to C₁₈aryl, preferably C₁to C₄alkyl or substituted or unsubstituted C₆to C₁₀aryl, more preferably methyl or unsubstituted or substituted phenyl,

and

the dotted lines are bonding sites.

More preferred ring structures formed by two adjacent residues are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

R^a, R^b, R^cand R^deach independently represents C₁to O₈alkyl or substituted or unsubstituted C₆to C₁₈aryl, preferably C₁to C₄alkyl or substituted or unsubstituted C₆to C₁₀aryl, more preferably methyl or unsubstituted or substituted phenyl,

and

the dotted lines are bonding sites.

Preferably, R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸each independently represents hydrogen; deuterium; an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted; CN; N(R²²)₂; OR²⁰; SR²⁰; B(R²¹)₂; or F;

R⁵and R⁶each independently represents an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted; an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted;

and

at least two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸together form a ring structure which is unsubstituted or substituted,

R¹and R¹⁸do not form together a ring structure;

and

(R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring.

More preferably, R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸each independently represents hydrogen; deuterium; an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted; N(R²²)₂; OR²⁰; or SR²⁰.

More preferably, R⁵and R⁶each independently represents an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted, most preferably methyl; or an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted, most preferably unsubstituted phenyl.

In addition, to the more preferred embodiments mentioned above,

at least two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸together form a ring structure which is unsubstituted or substituted,

R¹and R¹⁸do not form together a ring structure;

and

(R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring.

Most preferably, R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸each independently represents hydrogen; deuterium; an aryl group having from 6 to 18 ring carbon atoms, preferably 6 to 13 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18 ring atoms, preferably 5 to 13 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 8, preferably 1 to 4 carbon atoms which is unsubstituted or substituted, more preferably methyl, ethyl n-propyl, iso-propyl, n-butyl, tert.-butyl, s-butyl, isobutyl; a cycloalkyl group having from 3 to 10, preferably 5 or 6 ring carbon atoms which is unsubstituted or substituted; N(R²²)₂; OR²⁰; or SR²⁰.

Most preferably, R⁵and R⁶each independently represents an alkyl group having from 1 to 8, preferably 1 to 4 carbon atoms which is unsubstituted or substituted, more preferably methyl, ethyl n-propyl, iso-propyl, n-butyl, tert.-butyl, s-butyl, isobutyl; most preferably methyl; or an aryl group having from 6 to 18, preferably 6 to 13 ring carbon atoms which is unsubstituted or substituted, most preferably unsubstituted phenyl.

In addition, to the most preferred embodiments mentioned above,

Examples for ring structures formed by two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸are shown below (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

Preferred ring structures formed by two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

More preferred ring structures formed by two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 60, preferably from 6 to 30, more preferably from 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;

and/or

R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸forms a ring structure which is unsubstituted or substituted.

Preferably, R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;

and/or

R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴and/or R⁷, R⁸, R⁹and/or R¹⁰, R¹¹, R¹², R¹³, R¹⁴and/or R¹⁵, R¹⁶, R¹⁷, R¹⁸forms a ring structure which is unsubstituted or substituted.

Most preferably, R²⁰, R²¹, and R²²each independently represents an aryl group having from 6 to 18, preferably 6 to 13 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18, preferably 5 to 13 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted, more preferably methyl, ethyl n-propyl, iso-propyl, n-butyl, tert.-butyl, s-butyl, isobutyl; most preferably iso-propyl, tert.-butyl; or a cycloalkyl group having from 3 to 10, preferably 5 or 6 ring carbon atoms which is unsubstituted or substituted;

- and/or two residues R²²and/or two residues R²¹together form a ring structure which is unsubstituted or substituted;
- and/or R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴and/or R⁷, R⁸, R⁹and/or R¹⁰, R¹¹, R¹², R¹³, R¹⁴and/or R¹⁵, R¹⁶, R¹⁷, R¹⁸forms a ring structure which is unsubstituted or substituted.

Examples for ring structures formed by R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴and/or R⁷, R⁸, R⁹and/or R¹⁰, R¹¹, R¹², R¹³, R¹⁴and/or R¹⁵, R¹⁶, R¹⁷, R¹⁸are shown below (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, BR^c, S or NR^c,

X′ is N or CR^d,

X″ and Y″ each independently represents O, S, BR^cor NR^c,

X′″ is O, CR^aR^b, BR^c, S or NR^c,

R^cand R^deach independently represents H, C₁to C₈alkyl or substituted or unsubstituted C₆to C₁₈aryl, preferably C₁to C₄alkyl or substituted or unsubstituted C₆to C₁₀aryl, more preferably methyl or unsubstituted or substituted phenyl.

Preferred ring structures formed by formed by R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴and/or R⁷, R⁸, R⁹and/or R¹⁰, R¹¹, R¹², R¹³, R¹⁴and/or R¹⁵, R¹⁶, R¹⁷, R¹⁸are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

More preferred ring structures formed by formed by R²⁰, R²¹, and/or R²²together with an adjacent residue R¹, R², R³, R⁴and/or R⁷, R⁸, R⁹and/or R¹⁰, R¹¹, R¹², R¹³, R¹⁴and/or R¹⁵, R¹⁶, R¹⁷, R¹⁸are (the ring structures below are unsubstituted or substituted by one or more of the substituents mentioned above, preferably, the ring structures below are unsubstituted or substituted by one or two substituents selected form the group of substituents defined for R^a, R^b, R^cand R^d):

embedded image

wherein X is O, CR^aR^b, BR^c, S or NR^c,

X′ is N or CR^d,

R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²⁴and R²⁵together form a ring structure which is unsubstituted or substituted.

Preferably, R²⁴, R²⁵and R²⁶each independently represents an aryl group having from 6 to 18, preferably 6 to 13 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18, preferably 5 to 13 ring atoms which is unsubstituted or substituted and which is linked via a carbon atom to Si; an alkyl group having from 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted, more preferably methyl, ethyl n-propyl, isopropyl, n-butyl, tert.-butyl, s-butyl, isobutyl; most preferably methyl, iso-propyl, tert.-butyl; or a cycloalkyl group having from 3 to 10, preferably 5 or 6 ring carbon atoms which is unsubstituted or substituted.

The heterocyclic compounds of formula (I) are characterized in that the following features have to be fulfilled:

- at least two adjacent residues R¹, R², R³, R⁴and/or R⁵and/or at least two adjacent residues R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and/or R¹⁸together form a ring structure which is unsubstituted or substituted; and
- (R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring.

R¹and R¹⁸do not form together a ring structure.

Preferably, (R₉and R₁₀) and/or (R₁₄and R₁₅) are joined together via a direct bond or via O, S, BR²¹, NR²²or C(R²³)₂,

wherein

R²³represents H, an aryl group having from 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted; or a cycloalkyl group having from 3 to 20, preferably 3 to 10 ring carbon atoms which is unsubstituted or substituted;

and/or

two residues R²³together form a ring structure which is unsubstituted or substituted.

Preferably, R²³represents an aryl group having from 6 to 18, preferably 6 to 13 ring carbon atoms which is unsubstituted or substituted; a heteroaryl group having from 5 to 18, preferably 5 to 13 ring atoms which is unsubstituted or substituted; an alkyl group having from 1 to 8, more preferably 1 to 4 carbon atoms which is unsubstituted or substituted, more preferably methyl, ethyl n-propyl, iso-propyl, n-butyl, tert.-butyl, s-butyl, isobutyl; or a cycloalkyl group having from 3 to 10, preferably 5 or 6 ring carbon atoms which is unsubstituted or substituted.

Examples for the case that (R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together to form a ring shown by the following formulae (Ia), (Ib) and (Ic):

embedded image

wherein

X^aand X^beach independently represent a direct bond or O, S, BR²¹, NR²², C(R²³)₂, preferably a direct bond or O, S, NR²²or C(R²³)₂, more preferably a direct bond;

and the residues R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²¹, R²²and R²³are defined above.

More preferably, (R⁹and R¹⁰) and/or (R¹⁴and R¹⁵) are joined together via a direct bond.

The compounds of formula (I) are therefore more preferably characterized by the following formulae (Ia1), (Ib1) and (Ic1):

embedded image

wherein the residues R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸are defined above.

Most preferably, (R⁹and R¹⁰) or (R¹⁴and R¹⁵) are joined together to form a ring. Further most preferred compounds are therefore the compounds of formulae (Ia1) and (Ib1).

Compounds of formula (Ia1) and (Ib1) are further preferred, wherein:

- In the case of compounds of formula (Ia1):
- (R²and R³) or (R³and R⁴) or (R¹²and R¹³) together form a ring structure which is unsubstituted or substituted; suitable ring structures are mentioned above and in the exemplified compounds below; and
- In the case of compounds of formula (Ib1):
- (R¹¹and R¹²) or (R¹⁷and R¹⁸) together form a ring structure which is unsubstituted or substituted; suitable ring structures are mentioned above and in the exemplified compounds below.

In a preferred embodiment, the heterocyclic compounds of formula (I) preferably comprise 8 to 15 rings which are fused together, more preferably 8 to 13 rings as most preferably 8 to 11 rings which are fused together.

The molar mass of the heterocyclic compounds of formula (I) is preferably 435 g/mol to 2500 g/mol, more preferably 438 g/mol to 2000 g/mol, most preferably 438 g/mol to 1500 g/mol.

In a further preferred embodiment 4, 5, 6, 7, 8, 9 or 10, preferably 4, 5, 6, 7 or 8 of the residues R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷and R¹⁸are not hydrogen; i.e. the remaining residues are hydrogen.

Below, examples for compounds of formula (I) are given:

embedded image

Preparation of the Compounds of Formula (I)

The compounds represented by formula (I) can be synthesized in accordance with the reactions conducted in the examples of the present application, and by using alternative reactions or raw materials suited to an intended product, in analogy to reactions and raw materials known in the art.

The compounds of formula (I) are for example prepared by the following step:

- (i) Addition of BHal₃to the intermediate (IIa), (IIb) or (IIc), whereby the compound of formula (I) is obtained:

embedded image

wherein

Hal represents halogen, preferably Cl, Br or I, more preferably Cl or Br and most preferably Br;

Hal′ represents halogen, preferably Cl, Br or I, more preferably Cl or Br and most preferably Br; and

all other residues and indices are as defined before.

Suitable reaction conditions are mentioned in the examples of the present application.

The intermediates (IIa), (IIb) and (IIc) are for example prepared starting from a compound of formula (IIIa), (IIIb) or (IIIc)

embedded image

wherein

Hal′ represents halogen, preferably Cl, Br or I, more preferably Cl or Br and most preferably Br; and

all other residues and indices are as defined before.

Suitable reaction conditions are mentioned in the examples of the present application.

The intermediates (IIIa), (IIIb) and (IIIc) are for example prepared by the following step:

embedded image

Hal′ represents halogen, preferably Cl, Br or I, more preferably Cl or Br and most preferably Br;

Hal″ represents halogen or pseudohalogen, preferably F, Cl, Br, I or CF₃SO₃, more preferably F or Br;

“base” is any suitable base known by a person skilled in the art, preferably alkali metal carbonates like Li-, Na-, K-, Rb- or Cs carbonate, alkaline earth metal carbonates like Mg or Ca carbonates, alkali metal alkoxylates like NaOtBu or KOtBu, or bis(trimethylsilyl)amide; more preferably alkali metal carbonates like Li-, Na-, K-, Rb- or Cs carbonate or alkali metal alkoxylates; most preferably Cs carbonate, NaOtBu or KOtBu;

“Pd catalyst” is any suitable catalyst useful for a Buchwald coupling, e.g. a palladium complex comprising phosphine ligands, like PdCl₂(dppf), Pd[P(p-tol)₃]₂; Pd(OAc)₂or Pd₂(dba)₃;

and

all other residues and indices are as defined before.

dba is tris(dibenzylideneacetone)dipalladium(0)

OAc is CH₃—C(═O)

tol is tolyl

dppf is 1,1′-ferrocenediyl-bis(diphenylphosphine)

Generally, in the case that Hal″ is F, no Pd catalyst is used.

Suitable reaction conditions are mentioned in the examples of the present application.

Examples for suitable preparation processes are mentioned below.

Organic Electroluminescence Device

According to one aspect of the present invention a material for an organic electroluminescence device comprising at least one compound of formula (I) is provided.

According to another aspect of the present invention, an organic electroluminescence device comprising at least one compound of formula (I) is provided.

According to another aspect of the invention, the following organic electroluminescence device is provided: An organic electroluminescence device comprising a cathode, an anode, and one or more organic thin film layers comprising a light emitting layer disposed between the cathode and the anode, wherein at least one layer of the organic thin film layers comprises at least one compound of formula (I).

According to another aspect of the invention an organic electroluminescence device is provided, wherein the light emitting layer comprises at least one compound of formula (I).

According to another aspect of the invention an organic electroluminescence device is provided, wherein the light emitting layer comprises at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

According to another aspect of the invention an electronic equipment provided with the organic electroluminescence device according to the present invention is provided.

According to another aspect of the invention an emitter material is provided comprising at least one compound of formula (I).

According to another aspect of the invention a light emitting layer is provided comprising at least one host and at least one dopant, wherein the dopant comprises at least one compound of formula (I).

According to another aspect of the invention the use of a compound of formula (I) according to the present invention in an organic electroluminescence device is provided.

In one embodiment, the organic EL device comprises a hole-transporting layer between the anode and the emitting layer.

In one embodiment, the organic EL device comprises an electron-transporting layer between the cathode and the emitting layer.

In the present specification, regarding the “one or more organic thin film layers between the emitting layer and the anode”, if only one organic layer is present between the emitting layer and the anode, it means that layer, and if plural organic layers are present, it means at least one layer thereof. For example, if two or more organic layers are present between the emitting layer and the anode, an organic layer nearer to the emitting layer is called the “hole-transporting layer”, and an organic layer nearer to the anode is called the “hole-injecting layer”. Each of the “hole-transporting layer” and the “hole-injecting layer” may be a single layer or may be formed of two or more layers. One of these layers may be a single layer and the other may be formed of two or more layers.

Similarly, regarding the “one or more organic thin film layers between the emitting layer and the cathode”, if only one organic layer is present between the emitting layer and the cathode, it means that layer, and if plural organic layers are present, it means at least one layer thereof. For example, if two or more organic layers are present between the emitting layer and the cathode, an organic layer nearer to the emitting layer is called the “electron-transporting layer”, and an organic layer nearer to the cathode is called the “electron-injecting layer”. Each of the “electron-transporting layer” and the “electron-injecting layer” may be a single layer or may be formed of two or more layers. One of these layers may be a single layer and the other may be formed of two or more layers.

The “one or more organic thin film layers comprising an emitting layer” mentioned above, preferably the emitting layer, comprises a compound represented by formula (I). The compound represented by formula (I) preferably functions as an emitter material, more preferably as a fluorescent emitter material, most preferably as a blue fluorescent emitter material. By the presence of a compound of formula (I) in the organic EL device, preferably in the emitting layer, organic EL devices characterized by high external quantum efficiencies (EQE) and long lifetimes are provided.

According to another aspect of the invention, an emitting layer of the organic electroluminescence device is provided which comprises at least one compound of formula (I).

Preferably, the emitting layer comprises at least one emitting material (dopant material) and at least one host material, wherein the emitting material is at least one compound of formula (I).

Preferred host materials are substituted or unsubstituted polyaromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds.

More preferably, the organic electroluminescence device according to the present invention comprises in the emitting layer at least one compound of formula (I) as a dopant material and at least one host material selected from the group consisting of substituted or unsubstituted polyaromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, and substituted or unsubstituted pyrene compounds. Preferably, the at least one host is at least one substituted or unsubstituted anthracene compound.

According to another aspect of the invention, an emitting layer of the organic electroluminescence device is provided which comprises at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

Suitable anthracene compounds are represented by the following formula (10):

embedded image

wherein

one or more pairs of two or more adjacent R₁₀₁to R₁₁₀may form a substituted or unsubstituted, saturated or unsaturated ring;

R₁₀₁to R₁₁₀that do not form the substituted or unsubstituted, saturated or unsaturated ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted haloalkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group including 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group including 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group including 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 50 ring carbon atoms, a substituted or unsubstituted arylthio group including 6 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group including 7 to 50 carbon atoms, —Si(R₁₂₁)(R₁₂₂)(R₁₂₃), —C(═O)R₁₂₄, —COOR₁₂₅, —N(R₁₂₆)(R₁₂₇), a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms, or a group represented by the following formula (31);

R₁₂₁to R₁₂₇are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms; when each of R₁₂₁to R₁₂₇is present in plural, each of the plural R₁₂₁to R₁₂₇may be the same or different;

provided that at least one of R₁₀₁to R₁₁₀that do not form the substituted or unsubstituted, saturated or unsaturated ring is a group represented by the following formula (31). If two or more groups represented by the formula (31) are present, each of these groups may be the same or different;

-L₁₀₁-Ar₁₀₁ (31)

wherein in the formula (31),

L₁₀₁is a single bond, a substituted or unsubstituted arylene group including 6 to 30 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group including 5 to 30 ring atoms; Ar₁₀₁is a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms.

Specific examples of each substituent, substituents for “substituted or unsubstituted” and the halogen atom in the compound (10) are the same as those mentioned above.

An explanation will be given on “one or more pairs of two or more adjacent R₁₀₁to R₁₁₀may form a substituted or unsubstituted, saturated or unsaturated ring”.

The “one pair of two or more adjacent R₁₀₁to R₁₁₀” is a combination of R₁₀₁and R₁₀₂, R₁₀₂and R₁₀₃, R₁₀₃and R₁₀₄, R₁₀₅and R₁₀₆, R₁₀₆and R₁₀₇, R₁₀₇and R₁₀₈, R₁₀₈and R₁₀₉, R₁₀₁and R₁₀₂and R₁₀₃or the like, for example.

The substituent in “substituted” in the “substituted or unsubstituted” for the saturated or unsaturated ring is the same as those for “substituted or unsubstituted” mentioned in the formula (10).

The “saturated or unsaturated ring” means, when R₁₀₁and R₁₀₂form a ring, for example, a ring formed by a carbon atom with which R₁₀₁is bonded, a carbon atom with which R₁₀₂is bonded and one or more arbitrary elements. Specifically, when a ring is formed by R₁₀₁and R₁₀₂, when an unsaturated ring is formed by a carbon atom with which R₁₀₁is bonded, a carbon atom with R₁₀₂is bonded and four carbon atoms, the ring formed by R₁₀₁and R₁₀₂is a benzene ring.

The “arbitrary element” is preferably a C element, a N element, an O element or a S element. In the arbitrary element (C element or N element, for example), atomic bondings that do not form a ring may be terminated by a hydrogen atom, or the like.

The “one or more arbitrary element” 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 arbitrary elements.

For example, R₁₀₁and R₁₀₂may form a ring, and simultaneously, R₁₀₅and R₁₀₆may form a ring. In this case, the compound represented by the formula (10) is a compound represented by the following formula (10A), for example:

embedded image

In one embodiment, R₁₀₁to R₁₁₀are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms or a group represented by the formula (31).

Preferably, R₁₀₁to R₁₁₀are independently a hydrogen atom, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms or a group represented by the formula (31).

More preferably, R₁₀₁to R₁₁₀are independently a hydrogen atom, a substituted or unsubstituted aryl group including 6 to 18 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 18 ring atoms or a group represented by the formula (31).

Most preferably, at least one of R₁₀₉and R₁₁₀is a group represented by the formula (31).

Further most preferably, R₁₀₉and R₁₁₀are independently a group represented by the formula (31).

In one embodiment, the compound (10) is a compound represented by the following formula (10-1):

embedded image

wherein in the formula (10-1), R₁₀₁to R₁₀₈, L₁₀₁and Ar₁₀₁are as defined in the formula (10).

In one embodiment, the compound (10) is a compound represented by the following formula (10-2):

embedded image

wherein in the formula (10-2), R₁₀₁, R₁₀₃to R₁₀₈, L₁₀₁and Ar₁₀₁are as defined in the formula (10).

In one embodiment, the compound (10) is a compound represented by the following formula (10-3):

embedded image

wherein in the formula (10-3),

R_101Ato R_108Aare independently a hydrogen atom or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms;

L_101Ais a single bond or a substituted or unsubstituted arylene group including 6 to 30 ring carbon atoms, and the two L_101As may be the same or different;

Ar_101Ais a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, and the two Ar_101As may be the same or different.

In one embodiment, the compound (10) is a compound represented by the following formula (10-4):

embedded image

wherein in the formula (10-4),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare independently a hydrogen atom or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms;

X₁₁is O, S, or N(R₆₁);

R₆₁is a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms; one of R₆₂to R₆₉is an atomic bonding that is bonded with L₁₀₁;

- one or more pairs of adjacent R₆₂to R₆₉that are not bonded with L₁₀₁may be bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring; and
  
  R₆₂to R₆₉that are not bonded with L₁₀₁and do not form the substituted or unsubstituted, saturated or unsaturated ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

In one embodiment, the compound (10) is a compound represented by the following formula (10-4A):

embedded image

wherein in the formula (10-4A),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare independently a hydrogen atom or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms;

X₁₁is O, S or N(R₆₁);

R₆₁is a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms;

one or more pairs of adjacent two or more of R_62Ato R_69Amay form a substituted or unsubstituted, saturated or unsaturated ring, and adjacent two of R_62Ato R_69Aform a ring represented by the following formula (10-4A-1); and

R_62Ato R_69Athat do not form a substituted or unsubstituted, saturated or unsaturated ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

embedded image

wherein in the formula (10-4A-1),

each of the two atomic bondings * is bonded with adjacent two of R_62Ato R_69A;

one of R₇₀to R₇₃is an atomic bonding that is bonded with L₁₀₁; and

R₇₀to R₇₃that are not bonded with L₁₀₁are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

In one embodiment, the compound (10) is a compound represented by the following formula (10-6):

embedded image

wherein in the formula (10-6),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare as defined in the formula (10-4);

R₆₆to R₆₉are as defined in the formula (10-4); and

X₁₂is O or S.

In one embodiment, the compound represented by the formula (10-6) is a compound represented by the following formula (10-6H):

embedded image

wherein in the formula (10-6H),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R₆₆to R₆₉are as defined in the formula (10-4); and

X₁₂is O or S.

In one embodiment, the compound represented by the formulae (10-6) and (10-6H) is a compound represented by the following formula (10-6Ha):

embedded image

wherein in the formula (10-6Ha),

L₁₀₁and Ar₁₀₁are as defined in the formula (10); and

X₁₂is O or S.

In one embodiment, the compound represented by the formulae (10-6), (10-6H) and (10-6Ha) is a compound represented by the following formula (10-6Ha-1) or (10-6Ha-2):

embedded image

wherein in the formula (10-6Ha-1) and (10-6Ha-2),

L₁₀₁and Ar₁₀₁are as defined in the formula (10); and

X₁₂is O or S.

In one embodiment, the compound (10) is a compound represented by the following formula (10-7):

embedded image

wherein in the formula (10-7),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare as defined in the formula (10-4);

X₁₁is as defined in the formula (10-4); and

R₆₂to R₆₉are as defined in the formula (10-4), provided that any one pair of R₆₆and R₆₇, R₆₇and R₆₈, and R₆₈and R₆₉are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring.

In one embodiment, the compound (10) is a compound represented by the following formula (10-7H):

embedded image

wherein in the formula (10-7H),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

X₁₁is as defined in the formula (10-4); and

R₆₂to R₆₉are as defined in the formula (10-4), provided that any one pair of R₆₆and R₆₇, R₆₇and R₆₈, and R₆₈and R₆₉are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring.

In one embodiment, the compound (10) is a compound represented by the following formula (10-8):

embedded image

wherein in the formula (10-8),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare as defined in the formula (10-4);

X₁₂is O or S; and

In one embodiment, the compound represented by the formula (10-8) is a compound represented by the following formula (10-8H):

embedded image

In the formula (10-8H), L₁₀₁and Ar₁₀₁are as defined in the formula (10).

R₆₆to R₆₉are as defined in the formula (10-4), provided that any one pair of R₆₆and R₆₇, R₆₇and R₆₈, as well as R₆₈and R₆₉are bonded with each other to form a substituted or unsubstituted, saturated or unsaturated ring. Any one pair of R₆₆and R₆₇, R₆₇and R₆₈, as well as R₆₈and R₆₉may preferably be bonded with each other to form an unsubstituted benzene ring; and

X₁₂is O or S.

In one embodiment, as for the compound represented by the formula (10-7), (10-8) or (10-8H), any one pair of R₆₆and R₆₇, R₆₇and R₆₈, as well as R₆₈and R₆₉are bonded with each other to form a ring represented by the following formula (10-8-1) or (10-8-2), and R₆₆to R₆₉that do not form the ring represented by the formula (10-8-1) or (10-8-2) do not form a substituted or unsubstituted, saturated or unsaturated ring.

embedded image

wherein in the formulae (10-8-1) and (10-8-2),

the two atomic bondings * are independently bonded with one pair of R₆₆and R₆₇, R₆₇and R₆₈, or R₆₈and R₆₉;

R₈₀to R₈₃are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms; and

X₁₃is O or S.

In one embodiment, the compound (10) is a compound represented by the following formula (10-9):

embedded image

wherein in the formula (10-9),

L₁₀₁and Ar₁₀₁are as defined in the formula (10);

R_101Ato R_108Aare as defined in the formula (10-4);

R₆₆to R₆₉are as defined in the formula (10-4), provided that R₆₆and R₆₇, R₆₇and Res, as well as R₆₈and R₆₉are not bonded with each other and do not form a substituted or unsubstituted, saturated or unsaturated ring; and

X₁₂is O or S.

In one embodiment, the compound (10) is selected from the group consisting of compounds represented by the following formulae (10-10-1) to (10-10-4).

embedded image

In the formulae (10-10-1H) to (10-10-4H), L_101Aand Ar_101Aare as defined in the formula (10-3).

In one embodiment, in the compound represented by the formula (10-1), at least one Ar₁₀₁is a monovalent group having a structure represented by the following formula (50).

embedded image

In the formula (50),

X₁₅₁is O, S, or C(R₁₆₁)(R₁₆₂).

One of R₁₅₁to R₁₆₀is a single bond which bonds with L₁₀₁.

One or more sets of adjacent two or more of R₁₅₁to R₁₅₄and one or more sets of adjacent two or more of R₁₅₅to R₁₆₀, which are not a single bond which bonds with L₁₀₁, form a substituted or unsubstituted, saturated or unsaturated ring by bonding with each other, or do not form a substituted or unsubstituted, saturated or unsaturated ring.

R₁₆₁and R₁₆₂form a substituted or unsubstituted, saturated or unsaturated ring by bonding with each other, or do not form a substituted or unsubstituted, saturated or unsaturated ring.

R₁₆₁and R₁₆₂which do not form the substituted or unsubstituted, saturated or unsaturated ring, and R₁₅₁to R₁₆₀which are not a single bond which bonds with L₁₀₁and do not form the substituted or unsubstituted, saturated or unsaturated ring are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted haloalkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group including 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group including 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group including 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 50 ring carbon atoms, a substituted or unsubstituted arylthio group including 6 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group including 7 to 50 carbon atoms, —Si(R121)(R122)(R123), —C(═O)R124, —COOR125, —N(R126)(R127), a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms.

Ar₁₀₁, which is not a monovalent group having the structure represented by the formula (50) is a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group including 5 to 50 ring atoms.

The position to be the single bond which bonds with L₁₀₁in the formula (50) is not particularly limited. In one embodiment, one of R₁₅₁to R₁₆₀in the formula (50) is a single bond which bonds with L₁₀₁.

In one embodiment, Ar₁₀₁is a monovalent group represented by the following formula (50-R₁₅₂), (50-R₁₅₃), (50-R₁₅₄), (50-R₁₅₇), or (50-R₁₅₈).

embedded image

In the formulas (50-R₁₅₂), (50-R₁₅₃), (50-R₁₅₄), (50-R₁₅₇), and (50-R₁₅₈), X₁₅₁, R₁₅₁to R₁₆₀are as defined in the formula (50).

* is a single bond which bonds with L₁₀₁.

As for the compound represented by the formula (10), the following compounds can be given as specific examples. The compound represented by the formula (10) is not limited to these specific examples. In the following specific examples, “D” represents a deuterium atom.

embedded image

embedded image

embedded image

embedded image

embedded image

In the case that the emitting layer comprises the compound represented by formula (I) as a dopant and at least one host, wherein preferred hosts are mentioned above, and the host is more preferably at least one compound represented by formula (10), the content of the at least one compound represented by formula (I) is preferably 0.5 mass % to 70 mass %, more preferably 0.5 to 30 mass %, further preferably 1 to 30 mass %, still further preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass %, further particularly preferably 1 to 5 mass %, relative to the entire mass of the emitting layer.

The content of the at least one host, wherein preferred hosts are mentioned above, preferably the at least one compound represented by formula (10) is preferably 30 mass % to 99.9 mass %, more preferably 70 to 99.5 mass %, further preferably 70 to 99 mass %, still further preferably 80 to 99 mass %, and particularly preferably 90 to 99 mass %, further particularly preferably 95 to 99 mass %, relative to the entire mass of the emitting layer.

An Explanation Will be Made on the Layer Configuration of the Organic EL Device According to One Aspect of the Invention.

An organic EL device according to one aspect of the invention comprises a cathode, an anode, and one or more organic thin film layers comprising an emitting layer disposed between the cathode and the anode. The organic layer comprises at least one layer composed of an organic compound. Alternatively, the organic layer is formed by laminating a plurality of layers composed of an organic compound. The organic layer may further comprise an inorganic compound in addition to the organic compound.

At least one of the organic layers is an emitting layer. The organic layer may be constituted, for example, as a single emitting layer, or may comprise other layers which can be adopted in the layer structure of the organic EL device. The layer that can be adopted in the layer structure of the organic EL device is not particularly limited, but examples thereof include a hole-transporting zone (comprising at least one hole-transporting layer and preferably in addition at least one of a hole-injecting layer, an electron-blocking layer, an exciton-blocking layer, etc.), an emitting layer, a spacing layer, and an electron-transporting zone (comprising at least one electron-transporting layer and preferably in addition at least one of an electron-injecting layer, a hole-blocking layer, etc.) provided between the cathode and the emitting layer.

The organic EL device according to one aspect of the invention may be, for example, a fluorescent or phosphorescent monochromatic light emitting device or a fluorescent/phosphorescent hybrid white light emitting device. Preferably, the organic EL device is a fluorescent monochromatic light emitting device, more preferably a blue fluorescent monochromatic light emitting device or a fluorescent/phosphorescent hybrid white light emitting device. Blue fluorescence means a fluorescence at 400 to 500 nm (peak maximum), preferably at 430 nm to 490 nm (peak maximum).

Further, it may be a simple type device having a single emitting unit or a tandem type device having a plurality of emitting units.

The “emitting unit” in the specification is the smallest unit that comprises organic layers, in which at least one of the organic layers is an emitting layer and light is emitted by recombination of injected holes and electrons.

In addition, the “emitting layer” described in the present specification is an organic layer having an emitting function. The emitting layer is, for example, a phosphorescent emitting layer, a fluorescent emitting layer or the like, preferably a fluorescent emitting layer, more preferably a blue fluorescent emitting layer, and may be a single layer or a stack of a plurality of layers.

The emitting unit may be a stacked type unit having a plurality of phosphorescent emitting layers or fluorescent emitting layers. In this case, for example, a spacing layer for preventing excitons generated in the phosphorescent emitting layer from diffusing into the fluorescent emitting layer may be provided between the respective light-emitting layers.

As the simple type organic EL device, a device configuration such as anode/emitting unit/cathode can be given.

Examples for representative layer structures of the emitting unit are shown below. The layers in parentheses are provided arbitrarily.

- (a) (Hole-injecting layer/) Hole-transporting layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (b) (Hole-injecting layer/) Hole-transporting layer/Phosphorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (c) (Hole-injecting layer/) Hole-transporting layer/First fluorescent emitting layer/Second fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (d) (Hole-injecting layer/) Hole-transporting layer/First phosphorescent layer/Second phosphorescent layer (/Electron-transporting layer/Electron-injecting layer)
- (e) (Hole-injecting layer/) Hole-transporting layer/Phosphorescent emitting layer/Spacing layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (f) (Hole-injecting layer/) Hole-transporting layer/First phosphorescent emitting layer/Second phosphorescent emitting layer/Spacing layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (g) (Hole-injecting layer/) Hole-transporting layer/First phosphorescent layer/Spacing layer/Second phosphorescent emitting layer/Spacing layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (h) (Hole-injecting layer/) Hole-transporting layer/Phosphorescent emitting layer/Spacing layer/First fluorescent emitting layer/Second fluorescent emitting layer (/Electron-transporting Layer/Electron-injecting Layer)
- (i) (Hole-injecting layer/) Hole-transporting layer/Electron-blocking layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (j) (Hole-injecting layer/) Hole-transporting layer/Electron-blocking layer/Phosphorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (k) (Hole-injecting layer/) Hole-transporting layer/Exciton-blocking layer/Fluorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (l) (Hole-injecting layer/) Hole-transporting layer/Exciton-blocking layer/Phosphorescent emitting layer (/Electron-transporting layer/Electron-injecting layer)
- (m) (Hole-injecting layer/) First hole-transporting Layer/Second hole-transporting Layer/Fluorescent emitting layer (/Electron-transporting layer/electron-injecting Layer)
- (n) (Hole-injecting layer/) First hole-transporting layer/Second hole-transporting layer/Fluorescent emitting layer (/First electron-transporting layer/Second electron-transporting layer/Electron-injection layer)
- (o) (Hole-injecting layer/) First hole-transporting layer/Second hole-transporting layer/Phosphorescent emitting layer (/Electron-transporting layer/Electron-injecting Layer)
- (p) (Hole-injecting layer/) First hole-transporting layer/Second hole-transporting layer/Phosphorescent emitting layer (/First electron-transporting Layer/Second electron-transporting layer/Electron-injecting layer)
- (q) (Hole-injecting layer/) Hole-transporting layer/Fluorescent emitting layer/Hole-blocking layer (/Electron-transporting layer/Electron-injecting layer)
- (r) (Hole-injecting layer/) Hole-transporting layer/Phosphorescent emitting layer/Hole-blocking layer (/Electron-transport layer/Electron-injecting layer)
- (s) (Hole-injecting layer/) Hole-transporting layer/Fluorescent emitting layer/Exciton-blocking layer (/Electron-transporting layer/Electron-injecting layer)
- (t) (Hole-injecting layer/) Hole-transporting layer/Phosphorescent emitting layer/Exciton-blocking layer (/Electron-transporting layer/Electron-injecting layer)

The layer structure of the organic EL device according to one aspect of the invention is not limited to the examples mentioned above.

For example, when the organic EL device has a hole-injecting layer and a hole-transporting layer, it is preferred that a hole-injecting layer be provided between the hole-transporting layer and the anode. Further, when the organic EL device has an electron-injecting layer and an electron-transporting layer, it is preferred that an electron-injecting layer be provided between the electron-transporting layer and the cathode. Further, each of the hole-injecting layer, the hole-transporting layer, the electron-transporting layer and the electron-injecting layer may be formed of a single layer or be formed of a plurality of layers.

The plurality of phosphorescent emitting layer, and the plurality of the phosphorescent emitting layer and the fluorescent emitting layer may be emitting layers that emit mutually different colors. For example, the emitting unit (f) may include a hole-transporting layer/first phosphorescent layer (red light emission)/second phosphorescent emitting layer (green light emission)/spacing layer/fluorescent emitting layer (blue light emission)/electron-transporting layer.

An electron-blocking layer may be provided between each light emitting layer and the hole-transporting layer or the spacing layer. Further, a hole-blocking layer may be provided between each emitting layer and the electron-transporting layer. By providing the electron-blocking layer or the hole-blocking layer, it is possible to confine electrons or holes in the emitting layer, thereby to improve the recombination probability of carriers in the emitting layer, and to improve light emitting efficiency.

As a representative device configuration of a tandem type organic EL device, for example, a device configuration such as anode/first emitting unit/intermediate layer/second emitting unit/cathode can be given.

The first emitting unit and the second emitting unit are independently selected from the above-mentioned emitting units, for example.

The intermediate layer is also generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generating layer, an electron withdrawing layer, a connecting layer, a connector layer, or an intermediate insulating layer. The intermediate layer is a layer that supplies electrons to the first emitting unit and holes to the second emitting unit, and can be formed from known materials.

FIG. 1 shows a schematic configuration of one example of the organic EL device of the invention. The organic EL device 1 comprises a substrate 2, an anode 3, a cathode 4 and an emitting unit 10 provided between the anode 3 and the cathode 4. The emitting unit 10 comprises an emitting layer 5 preferably comprising a host material and a dopant. A hole injecting and transporting layer 6 or the like may be provided between the emitting layer 5 and the anode 3 and an electron injecting layer 8 and an electron transporting layer 7 or the like (electron injecting and transporting unit 11) may be provided between the emitting layer 5 and the cathode 4. An electron-barrier layer may be provided on the anode 3 side of the emitting layer 5 and a hole-barrier layer may be provided on the cathode 4 side of the emitting layer 5. Due to such configuration, electrons or holes can be confined in the emitting layer 5, whereby possibility of generation of excitons in the emitting layer 5 can be improved.

Hereinbelow, an Explanation Will be Made on Function, Materials, Etc. Of Each Layer Constituting the Organic EL Device Described in the Present Specification.

(Substrate)

The substrate is used as a support of the organic EL device. The substrate preferably has a light transmittance of 50% or more in the visible light region with a wavelength of 400 to 700 nm, and a smooth substrate is preferable. Examples of the material of the substrate include soda-lime glass, aluminosilicate glass, quartz glass, plastic and the like. As a substrate, a flexible substrate can be used. The flexible substrate means a substrate that can be bent (flexible), and examples thereof include a plastic substrate and the like. Specific examples of the material for forming the plastic substrate include polycarbonate, polyallylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, polyethylene naphthalate and the like. Also, an inorganic vapor deposited film can be used.

(Anode)

As the anode, for example, it is preferable to use a metal, an alloy, a conductive compound, a mixture thereof or the like and having a high work function (specifically, 4.0 eV or more). Specific examples of the material of the anode include indium oxide-tin oxide (ITO: Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide or zinc oxide, graphene and the like. In addition, it is also possible to use gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (e.g. titanium oxide).

The anode is normally formed by depositing these materials on the substrate by a sputtering method. For example, indium oxide-zinc oxide can be formed by a sputtering method by using a target in which 1 to 10 mass % zinc oxide is added relative to indium oxide. Further, indium oxide containing tungsten oxide or zinc oxide can be formed by a sputtering method by using a target in which 0.5 to 5 mass % of tungsten oxide or 0.1 to 1 mass % of zinc oxide is added relative to indium oxide.

As other methods for forming the anode, a vacuum deposition method, a coating method, an inkjet method, a spin coating method or the like can be given. When silver paste or the like is used, it is possible to use a coating method, an inkjet method or the like.

The hole-injecting layer formed in contact with the anode is formed by using a material that allows easy hole injection regardless of the work function of the anode. For this reason, in the anode, it is possible to use a common electrode material, e.g. a metal, an alloy, a conductive compound and a mixture thereof. Specifically, a material having a small work function such as alkaline metals such as lithium and cesium; alkaline earth metals such as calcium and strontium; alloys containing these metals (for example, magnesium-silver and aluminum-lithium); rare earth metals such as europium and ytterbium; and an alloy containing rare earth metals.

(Hole-Transporting Layer)/(Hole-Injecting Layer)

The hole-transporting layer is an organic layer that is formed between the emitting layer and the anode, and has a function of transporting holes from the anode to the emitting layer. If the hole-transporting layer is composed of plural layers, an organic layer that is nearer to the anode may often be defined as the hole-injecting layer. The hole-injecting layer has a function of injecting holes efficiently to the organic layer unit from the anode. Said hole injection layer is generally used for stabilizing hole injection from anode to hole transporting layer which is generally consist of organic materials. Organic material having good contact with anode or organic material with p-type doping is preferably used for the hole injection layer.

p-doping usually consists of one or more p-dopant materials and one or more matrix materials. Matrix materials preferably have shallower HOMO level and p-dopant preferably have deeper LUMO level to enhance the carrier density of the layer. Specific examples for p-dopants are the below mentioned acceptor materials. Suitable matrix materials are the hole transport materials mentioned below, preferably aromatic or heterocyclic amine compounds.

Acceptor materials, or fused aromatic hydrocarbon materials or fused heterocycles which have high planarity, are preferably used as p-dopant materials for the hole injection layer. Specific examples for acceptor materials are, quinone compounds with one or more electron withdrawing groups, such as F₄TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), and 1,2,3-tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane; hexa-azatriphenylene compounds with one or more electron withdrawing groups, such as hexa-azatriphenylene-hexanitrile; aromatic hydrocarbon compounds with one or more electron withdrawing groups; and aryl boron compounds with one or more electron withdrawing groups. Preferred p-dopants are quinone compounds with one or more electron withdrawing groups, such as F₄TCNQ, 1,2,3-Tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane.

The ratio of the p-type dopant is preferably less than 20% of molar ratio, more preferably less than 10%, such as 1%, 3%, or 5%, related to the matrix material.

The hole transporting layer is generally used for injecting and transporting holes efficiently, and aromatic or heterocyclic amine compounds are preferably used.

Specific examples for compounds for the hole transporting layer are represented by the general formula (H),

embedded image

wherein

Ar₁to Ar₃each independently represents substituted or unsubstituted aryl group having 5 to 50 carbon atoms or substituted or unsubstituted heterocyclic group having 5 to 50 cyclic atoms, preferably phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, triphenylenyl group, fluorenyl group, spirobifluorenyl group, indenofluorenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazole substituted aryl group, dibenzofuran substituted aryl group or dibenzothiophene substituted aryl group; two or more substituents selected among Ar¹to Ar³may be bonded to each other to form a ring structure, such as a carbazole ring structure, or a acridane ring structure.

Preferably, at least one of Ar₁to Ar₃have additional one aryl or heterocyclic amine substituent, more preferably Ar₁has an additional aryl amino substituent, at the case of that it is preferable that Ar₁represents substituted or unsubstituted biphenylene group, substituted or unsubstituted fluorenylene group. Specific examples for the hole transport material are

embedded image

and the like.

A second hole transporting layer is preferably inserted between the first hole transporting layer and the emitting layer to enhance device performance by blocking excess electrons or excitons. Specific examples for second hole transporting layer are the same as for the first hole transporting layer. It is preferred that second hole transporting layer has higher triplet energy to block triplet excitons, especially for phosphorescent devices, such as bicarbazole compounds, biphenylamine compounds, triphenylenyl amine compounds, fluorenyl amine compounds, carbazole substituted arylamine compounds, dibenzofuran substituted arylamine compounds, and dibenzothiophene substituted arylamine compounds.

(Emitting Layer)

The emitting layer is a layer containing a substance having a high emitting property (emitter material or dopant material). As the dopant material, various materials can be used. For example, a fluorescent emitting compound (fluorescent dopant), a phosphorescent emitting compound (phosphorescent dopant) or the like can be used. A fluorescent emitting compound is a compound capable of emitting light from the singlet excited state, and an emitting layer containing a fluorescent emitting compound is called a fluorescent emitting layer. Further, a phosphorescent emitting compound is a compound capable of emitting light from the triplet excited state, and an emitting layer containing a phosphorescent emitting compound is called a phosphorescent emitting layer.

Preferably, the emitting layer in the organic EL device of the present application comprises a compound of formula (I) as a dopant material.

The emitting layer preferably comprises at least one dopant material and at least one host material that allows it to emit light efficiently. In some literatures, a dopant material is called a guest material, an emitter or an emitting material. In some literatures, a host material is called a matrix material.

A single emitting layer may comprise plural dopant materials and plural host materials. Further, plural emitting layers may be present.

In the present specification, a host material combined with the fluorescent dopant is referred to as a “fluorescent host” and a host material combined with the phosphorescent dopant is referred to as the “phosphorescent host”. Note that the fluorescent host and the phosphorescent host are not classified only by the molecular structure. The phosphorescent host is a material for forming a phosphorescent emitting layer containing a phosphorescent dopant, but does not mean that it cannot be used as a material for forming a fluorescent emitting layer. The same can be applied to the fluorescent host.

In one embodiment, it is preferred that the emitting layer comprises the compound represented by formula (I) according to the present invention (hereinafter, these compounds may be referred to as the “compound (I)”). More preferably, it is contained as a dopant material. Further, it is preferred that the compound (I) be contained in the emitting layer as a fluorescent dopant. Even further, it is preferred that the compound (I) be contained in the emitting layer as a blue fluorescent dopant.

In one embodiment, no specific restrictions are imposed on the content of the compound (I) as the dopant material in the emitting layer. In respect of sufficient emission and concentration quenching, the content is preferably 0.5 to 70 mass %, more preferably 0.8 to 30 mass %, further preferably 1 to 30 mass %, still further preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass %, further particularly preferably 1 to 5 mass %, even further particularly preferably 2 to 4 mass %, related to the mass of the emitting layer.

(Fluorescent Dopant)

As a fluorescent dopant other than the compound (1), a fused polycyclic aromatic compound, a styrylamine compound, a fused ring amine compound, a boron-containing compound, a pyrrole compound, an indole compound, a carbazole compound can be given, for example. Among these, a fused ring amine compound, a boron-containing compound, carbazole compound is preferable.

As the fused ring amine compound, a diaminopyrene compound, a diaminochrysene compound, a diaminoanthracene compound, a diaminofluorene compound, a diaminofluorene compound with which one or more benzofuro skeletons are fused, or the like can be given.

As the boron-containing compound, a pyrromethene compound, a triphenylborane compound or the like can be given.

As a blue fluorescent dopant, pyrene compounds, styrylamine compounds, chrysene compounds, fluoranthene compounds, fluorene compounds, diamine compounds, triarylamine compounds and the like can be given, for example. Specifically, N,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenyamine (abbreviation: YGAPA), 4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBAPA) or the like can be given.

As a green fluorescent dopant, an aromatic amine compound or the like can be given, for example. Specifically, N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N-[9,10-bis(1,1′-biphenyl-2-yl)]-N-[4-(9H-carbazole-9-yl)phenyl]-N-phenylanthracene-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracene-9-amine (abbreviation: DPhAPhA) or the like can be given, for example.

As a red fluorescent dopant, a tetracene compound, a diamine compound or the like can be given. Specifically, N,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N′,N′-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD) or the like can be given.

(Phosphorescent Dopant)

As a phosphorescent dopant, a phosphorescent emitting heavy metal complex and a phosphorescent emitting rare earth metal complex can be given.

As the heavy metal complex, an iridium complex, an osmium complex, a platinum complex or the like can be given. The heavy metal complex is for example an ortho-metalated complex of a metal selected from iridium, osmium and platinum.

Examples of rare earth metal complexes include terbium complexes, europium complexes and the like. Specifically, tris(acetylacetonate)(monophenanthroline)terbium(III) (abbreviation: Tb(acac)₃(Phen)), tris(1,3-diphenyl-1,3-propandionate)(monophenanthroline)europium(II) (abbreviation: Eu(DBM)₃(Phen)), tris[1-(2-thenoyl)-3,3,3-trifluoroacetonate](monophenanthroline)europium(III) (abbreviation: Eu(TTA)₃(Phen)) or the like can be given. These rare earth metal complexes are preferable as phosphorescent dopants since rare earth metal ions emit light due to electronic transition between different multiplicity.

As a blue phosphorescent dopant, an iridium complex, an osmium complex, a platinum complex, or the like can be given, for example. Specifically, bis[2-(4′,6′-difluorophenyl)pyridinate-N,C2′]iridium(III) tetrakis(1-pyrazolyl)borate (abbreviation: Flr6), bis[2-(4′,6′-difluorophenyl) pyridinato-N,C2′]iridium(II) picolinate (abbreviation: Ir(CF₃ppy)₂(pic)), bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(II) acetylacetonate (abbreviation: Flracac) or the like can be given.

As a green phosphorescent dopant, an iridium complex or the like can be given, for example. Specifically, tris(2-phenylpyridinato-N,C2′) iridium(III) (abbreviation: Ir(ppy)₃), bis(1,2-diphenyl-1 H-benzimidazolato)iridium(III) acetylacetonate (abbreviation: Ir(pbi)₂(acac)), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: Ir(bzq)₂(acac)) or the like can be given.

As a red phosphorescent dopant, an iridium complex, a platinum complex, a terbium complex, a europium complex or the like can be given. Specifically, bis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C3′]iridium(II) acetylacetonate (abbreviation: Ir(btp)₂(acac)), bis(1-phenylisoquinolinato-N,C2′)iridium(III) acetylacetonate (abbreviation: Ir(piq)₂(acac)), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato-]iridium(II) (abbreviation: Ir(Fdpq)₂(acac)), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation PtOEP) or the like can be given.

As mentioned above, the emitting layer preferably comprises at least one compound (1) as a dopant.

(Host Material)

As host material, metal complexes such as aluminum complexes, beryllium complexes and zinc complexes; heterocyclic compounds such as indole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinoline compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, oxadiazole compounds, benzimidazole compounds, phenanthroline compounds; fused polyaromatic hydrocarbon (PAH) compounds such as a naphthalene compound, a triphenylene compound, a carbazole compound, an anthracene compound, a phenanthrene compound, a pyrene compound, a chrysene compound, a naphthacene compound, a fluoranthene compound; and aromatic amine compound such as triarylamine compounds and fused polycyclic aromatic amine compounds 40 can be given, for example. Plural types of host materials can be used in combination.

As a fluorescent host, a compound having a higher singlet energy level than a fluorescent dopant is preferable. For example, a heterocyclic compound, a fused aromatic compound or the like can be given. As a fused aromatic compound, an anthracene compound, a pyrene compound, a chrysene compound, a naphthacene compound or the like are preferable. An anthracene compound is preferentially used as blue fluorescent host.

In the case that compound (1) is employed as at least one dopant material, preferred host materials are substituted or unsubstituted polyaromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds, preferably substituted or unsubstituted anthracene compounds or substituted or unsubstituted pyrene compounds, more preferably substituted or unsubstituted anthracene compounds, most preferably anthracene compounds represented by formula (10), as mentioned above.

As a phosphorescent host, a compound having a higher triplet energy level as compared with a phosphorescent dopant is preferable. For example, a metal complex, a heterocyclic compound, a fused aromatic compound or the like can be given. Among these, an indole compound, a carbazole compound, a pyridine compound, a pyrimidine compound, a triazine compound, a quinolone compound, an isoquinoline compound, a quinazoline compound, a dibenzofuran compound, a dibenzothiophene compound, a naphthalene compound, a triphenylene compound, a phenanthrene compound, a fluoranthene compound or the like can be given.

(Electron-Transporting Layer)/(Electron-Injecting Layer)

The electron-transporting layer is an organic layer that is formed between the emitting layer and the cathode and has a function of transporting electrons from the cathode to the emitting layer. When the electron-transporting layer is formed of plural layers, an organic layer or an inorganic layer that is nearer to the cathode is often defined as the electron injecting layer (see for example layer 8 in FIG. 1, wherein an electron injecting layer 8 and an electron transporting layer 7 form an electron injecting and transporting unit 11). The electron injecting layer has a function of injecting electrons from the cathode efficiently to the organic layer unit. Preferred electron injection materials are alkali metal, alkali metal compounds, alkali metal complexes, the alkaline earth metal complexes and the rare earth metal complexes.

According to one embodiment, it is preferred that the electron-transporting layer further comprises one or more layer(s) like a second electron-transporting layer, an electron injection layer to enhance efficiency and lifetime of the device, a hole blocking layer, an exciton blocking layer or a triplet blocking layer.

According to one embodiment, it is preferred that an electron-donating dopant be contained in the interfacial region between the cathode and the emitting unit. Due to such a configuration, the organic EL device can have an increased luminance or a long life. Here, the electron-donating dopant means one having a metal with a work function of 3.8 eV or less. As specific examples thereof, at least one selected from an alkali metal, an alkali metal complex, an alkali metal compound, an alkaline earth metal, an alkaline earth metal complex, an alkaline earth metal compound, a rare earth metal, a rare earth metal complex and a rare earth metal compound or the like can be mentioned.

As the alkali metal, Li (work function: 2.9 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV) and the like can be given. One having a work function of 2.9 eV or less is particularly preferable. Among them, K, Rb and Cs are preferable. Rb or Cs is further preferable. Cs is most preferable. As the alkaline earth metal, Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV) and the like can be given. One having a work function of 2.9 eV or less is particularly preferable. As the rare-earth metal, Sc, Y, Ce, Tb, Yb and the like can be given. One having a work function of 2.9 eV or less is particularly preferable.

Examples of the alkali metal compound include an alkali oxide such as Li₂O, Cs₂O or K₂O, and an alkali halide such as LiF, NaF, CsF and KF. Among them, LiF, Li₂O and NaF are preferable.

Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixtures thereof such as Ba_xSr_1-xO (0<x<1) and Ba_xCa_1-xO (0<x<1). Among them, BaO, SrO and CaO are preferable. Examples of the rare earth metal compound include YbF₃, ScF₃, ScO₃, Y₂O₃, Ce₂O₃, GdF₃and TbF₃. Among these, YbF₃, ScF₃and TbF₃are preferable.

The alkali metal complexes, the alkaline earth metal complexes and the rare earth metal complexes are not particularly limited as long as they contain, as a metal ion, at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions. Meanwhile, preferred examples of the ligand include, but are not limited to, quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfluborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, and azomethines.

Regarding the addition form of the electron-donating dopant, it is preferred that the electron-donating dopant be formed in a shape of a layer or an island in the interfacial region. A preferred method for the formation is a method in which an organic compound (a light emitting material or an electron-injecting material) for forming the interfacial region is deposited simultaneously with deposition of the electron-donating dopant by a resistant heating deposition method, thereby dispersing the electron-donating dopant in the organic compound.

In a case where the electron-donating dopant is formed into the shape of a layer, the light-emitting material or electron-injecting material which serves as an organic layer in the interface is formed into the shape of a layer. After that, a reductive dopant is solely deposited by the resistant heating deposition method to form a layer preferably having a thickness of from 0.1 nm to 15 nm. In a case where the electron-donating dopant is formed into the shape of an island, the emitting material or the electron-injecting material which serves as an organic layer in the interface is formed into the shape of an island. After that, the electron-donating dopant is solely deposited by the resistant heating deposition method to form an island preferably having a thickness of from 0.05 nm to 1 nm. As the electron-transporting material used in the electron-transporting layer other than a compound of the formula (I), an aromatic heterocyclic compound having one or more hetero atoms in the molecule may preferably be used. In particular, a nitrogen-containing heterocyclic compound is preferable.

According to one embodiment, it is preferable that the electron-transporting layer comprises a nitrogen-containing heterocyclic metal chelate.

According to the other embodiment, it is preferable that the electron-transporting layer comprises a substituted or unsubstituted nitrogen containing heterocyclic compound. Specific examples of preferred heterocyclic compounds for the electron-transporting layer are, 6-membered azine compounds; such as pyridine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds, preferably pyrimidine compounds or triazine compounds; 6-membered fused azine compounds, such as quinolone compounds, isoquinoline compounds, quinoxaline compounds, quinazoline compounds, phenanthroline compounds, benzoquinoline compounds, benzoisoquinoline compounds, dibenzoquinoxaline compounds, preferably quinolone compounds, isoquinoline compounds, phenanthroline compounds; 5-membered heterocyclic compounds, such as imidazole compounds, oxazole compounds, oxadiazole compounds, triazole compounds, thiazole compounds, thiadiazole compounds; fused imidazole compounds, such as benzimidazole compounds, imidazopyridine compounds, naphthoimidazole compounds, benzimidazophenanthridine compounds, benzimidzobenzimidazole compounds, preferably benzimidazole compounds, imidazopyridine compounds or benzimidazophenanthridine compounds.

According to another embodiment, it is preferable the electron-transporting layer comprises a phosphine oxide compound represented as Ar_p1Ar_p2Ar_p3P═O.

Ar_p1to Ar_p3are the substituents of phosphor atom and each independently represent substituted or unsubstituted above mentioned aryl group or substituted or unsubstituted above mentioned heterocyclic group.

According to another embodiment, it is preferable that the electron-transporting layer comprises aromatic hydrocarbon compounds. Specific examples of preferred aromatic hydrocarbon compounds for the electron-transporting layer are, oligo-phenylene compounds, naphthalene compounds, fluorene compounds, fluoranthenyl group, anthracene compounds, phenanthrene compounds, pyrene compounds, triphenylene compounds, benzanthracene compounds, chrysene compounds, benzphenanthrene compounds, naphthacene compounds, and benzochrysene compounds, preferably anthracene compounds, pyrene compounds and fluoranthene compounds.

(Cathode)

For the cathode, a metal, an alloy, an electrically conductive compound, and a mixture thereof, each having a small work function (specifically, a work function of 3.8 eV or less) are preferably 40 used. Specific examples of a material for the cathode include an alkali metal such as lithium and cesium; an alkaline earth metal such as magnesium, calcium, and strontium; aluminum, an alloy containing these metals (for example, magnesium-silver, aluminum-lithium); a rare earth metal such as europium and ytterbium; and an alloy containing a rare earth metal.

The cathode is usually formed by a vacuum vapor deposition or a sputtering method. Further, in the case of using a silver paste or the like, a coating method, an inkjet method, or the like can be employed.

Moreover, various electrically conductive materials such as silver, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide, selected independently from the work function, can be used to form a cathode. These electrically conductive materials are made into films using a sputtering method, an inkjet method, a spin coating method, or the like.

(Insulating Layer)

In the organic EL device, pixel defects based on leakage or a short circuit are easily generated since an electric field is applied to a thin film. In order to prevent this, it is preferred to insert an insulating thin layer between a pair of electrodes. Examples of materials used in the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture thereof may be used in the insulating layer, and a laminate of a plurality of layers that include these materials can be also used for the insulating layer.

(Spacing Layer)

A spacing layer is a layer provided between a fluorescent emitting layer and a phosphorescent emitting layer when a fluorescent emitting layer and a phosphorescent emitting layer are stacked in order to prevent diffusion of excitons generated in the phosphorescent emitting layer to the fluorescent emitting layer or in order to adjust the carrier balance. Further, the spacing layer can be provided between the plural phosphorescent emitting layers.

Since the spacing layer is provided between the emitting layers, the material used for the spacing layer is preferably a material having both electron-transporting capability and hole-transporting capability. In order to prevent diffusion of the triplet energy in adjacent phosphorescent emitting layers, it is preferred that the spacing layer have a triplet energy of 2.6 eV or more. As the material used for the spacing layer, the same materials as those used in the above-mentioned hole-transporting layer can be given.

(Electron-Blocking Layer, Hole-Blocking Layer, Exciton-Blocking Layer)

An electron-blocking layer, a hole-blocking layer, an exciton (triplet)-blocking layer, and the like may be provided in adjacent to the emitting layer.

The electron-blocking layer has a function of preventing leakage of electrons from the emitting layer to the hole-transporting layer. The hole-blocking layer has a function of preventing leakage of holes from the emitting layer to the electron-transporting layer. In order to improve hole blocking capability, a material having a deep HOMO level is preferably used. The exciton-blocking layer has a function of preventing diffusion of excitons generated in the emitting layer to the adjacent layers and confining the excitons within the emitting layer. In order to improve triplet block capability, a material having a high triplet level is preferably used.

(Method for Forming a Layer)

The method for forming each layer of the organic EL device of the invention is not particularly limited unless otherwise specified. A known film-forming method such as a dry film-forming method, a wet film-forming method or the like can be used. Specific examples of the dry film-forming method include a vacuum deposition method, a sputtering method, a plasma method, an ion plating method, and the like. Specific examples of the wet film-forming method include various coating methods such as a spin coating method, a dipping method, a flow coating method, an inkjet method, and the like.

(Film Thickness)

The film thickness of each layer of the organic EL device of the invention is not particularly limited unless otherwise specified. If the film thickness is too small, defects such as pinholes are likely to occur to make it difficult to obtain a sufficient luminance. If the film thickness is too large, a high driving voltage is required to be applied, leading to a lowering in efficiency. In this respect, the film thickness is preferably 0.1 nm to 10 μm, and more preferably 5 nm to 0.2 μm.

(Electronic Apparatus (Electronic Equipment))

The present invention further relates to an electronic equipment (electronic apparatus) comprising the organic electroluminescence device according to the present application. Examples of the electronic apparatus include display parts such as an organic EL panel module; display devices of television sets, mobile phones, smart phones, and personal computer, and the like; and emitting devices of a lighting device and a vehicle lighting device.

EXAMPLES

Next, the invention will be explained in more detail in accordance with the following synthesis examples, examples, and comparative examples, which should not be construed as limiting the scope of the invention.

The percentages and ratios mentioned in the examples below—unless stated otherwise—are % by weight and weight ratios.

I SYNTHESIS EXAMPLES

All experiments are carried out in protective gas atmosphere.

Compound 1
Intermediate 1-1

embedded image

Intermediate 1-1

25 g (87 mmol) of (9-phenyl-9H-carbazol-2-yl)boronic acid, 33.6 g (174 mmol) of 2-chloro-3-fluorobenzoyl chloride and 92 g (433 mmol) of potassium phosphate were suspended in 500 ml of toluene, 250 ml of tetrahydrofuran and 125 ml of water. The mixture was evacuated and backfilled with argon 4 times. 10.06 g (8.70 mmol) of Pd(PPh₃)₄were added and the reaction mixture was heated to 80° C. for 20 hours. The cooled down reaction mixture was diluted with water and ethyl acetate, the phases were separated and the water phase was extracted twice with ethyl acetate. The combined organic phases were washed with water and brine, dried over magnesium sulfate, filtered and concentrated under vacuum. The isolated product was purified by column chromatography (heptane/ethyl acetate) to give 21.3 g (61% yield) of Intermediate 1-1.

1H NMR (300 MHz, Dichloromethane-d2) δ 8.24-8.17 (m, 2H), 7.97 (dd, J=1.5, 0.6 Hz, 1H), 7.68-7.42 (m, 8H), 7.41-7.28 (m, 3H), 7.23 (ddd, J=7.3, 1.7, 1.0 Hz, 1H).

Intermediate 1-2

embedded image

13.67 g (48.9 mmol) of 3,6-di-tert-butyl-9H-carbazole and 20.54 g (51.4 mmol) of Intermediate 1-1 were dissolved in 490 ml of dimethylsulfoxide. 31.9 g (98 mmol) of cesium carbonate were added. The reaction mixture was heated to 90° C. for 7 hours, then cooled down to room temperature and quenched with deionized water. The product was extracted with ethyl acetate 3 times, the combined organic phases were washed with water and brine, dried over magnesium sulfate, filtered and concentrated under vacuum. The isolated product was purified by column chromatography (heptane/ethyl acetate) to give 23.0 g (71% yield) of Intermediate 1-2.

1H NMR (300 MHz, Dichloromethane-d2) δ 8.29-8.21 (m, 2H), 8.17 (dd, J=2.1, 0.7 Hz, 2H), 7.98 (dd, J=1.5, 0.6 Hz, 1H), 7.79 (dd, J=8.2, 1.5 Hz, 1H), 7.69-7.54 (m, 8H), 7.53-7.43 (m, 4H), 7.35 (ddd, J=8.1, 6.8, 1.3 Hz, 1H), 7.00 (dd, J=8.6, 0.6 Hz, 2H), 1.47 (s, 18H).

Intermediate 1-3

embedded image

113 ml (113 mmol) of titanium(V) chloride (1 M in toluene) were added dropwise to 90 ml of dry dichloromethane at −30° C. Then 56.7 ml (113 mmol) of dimethylzinc (2M in toluene) were added dropwise at −25° C. The yellow suspension was stirred at −25° C. for 30 minutes. 4.67 g (7.08 mmol) of Intermediate 1-2 were dissolved in 80 ml of dry dichloromethane and added to former mixture dropwise at −25° C. with a dropping funnel under Argon. Then the reaction mixture was allowed to warm up to room temperature and stirred overnight. After 24 hours, the reaction mixture was quenched with deionized water and diluted with dichloromethane. The phases were separated and the water phase was extracted twice with dichloromethane. The combined organic phases were washed with water and brine, dried over magnesium sulfate, filtered and concentrated under vacuum. The crude product was dissolved in dichloromethane and precipitated with ethanol. The solid formed was crushed, sonicated for 1 hour and then stirred overnight at room temperature. The beige precipitate was washed with ethanol and dried at 60° C./125 mbar. The isolated product was purified by column chromatography (dichloromethane) to give 4.6 g (purity: 65%, 61% yield) of Intermediate 1-3.

LC-MS: 671.3 (M−H)

Compound 1

embedded image

2.11 g (3.14 mmol) of Intermediate 1-3 were dissolved in 90 ml of water-free tert-butylbenzene. 3.31 ml (6.28 mmol) of tert-butyllithium (1.9 M in pentane) were slowly added at room temperature, then it was heated to 80° C. and stirred for 3 hours. The yellowish solution was cooled down to −30° C. and 0.59 ml (6.28 mmol) of tribromoborane were added. The reaction mixture was warmed up to room temperature, stirred for 2 hours and then cooled down to 0° C. 1.09 ml (6.28 mmol) of N,N-diisopropylethylamine were added and the reaction mixture was heated to 165° C. for 20 hours. 2.74 ml (15.71 mmol) of N,N-diisopropylethylamine were added again and the reaction mixture was heated to 165° C. for another 18 hours. The yellow suspension was cooled down to room temperature, quenched with 10% aqueous sodium acetate solution and extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated under vacuum. The isolated solid was purified by column chromatography (dichloromethane). The product was dissolved in dichloromethane, then 2-propanol was added and dichloromethane was distilled off. The resulting suspension was filtered, the solid washed with 2-propanol and dried to give 0.376 g (12% yield) of Compound 1 as a yellow solid.

1H NMR (300 MHz, Dichloromethane-d2) δ 9.43 (s, 1H), 9.11 (d, J=1.9 Hz, 1H), 8.61 (d, J=1.9 Hz, 1H), 8.47 (d, J=8.3 Hz, 1H), 8.40-8.33 (m, 2H), 8.26 (dt, J=7.6, 1.1 Hz, 1H), 7.91-7.83 (m, 2H), 7.76-7.66 (m, 6H), 7.62-7.53 (m, 1H), 7.48-7.42 (m, 2H), 7.40-7.32 (m, 1H), 1.86 (s, 6H), 1.72 (s, 9H), 1.54 (s, 9H).

Compound 2
Intermediate 2-1

embedded image

To a 91 mL (274 mmol) solution of methylmagensium iodide 3.0M in 67 mL diethyl ether was added dropwise a solution of 21 g (90 mmol) of methyl 2-bromo-3-fluorobenzoate in 34 mL diethyl ether at room temperature. After the end of the addition, the reaction was stirred for 45 min at room temperature, then poured onto 400 mL saturated ammonium chloride solution. The mixture was extracted with ethyl acetate 3 times, and the combined organic extracts were washed with saturated sodium bicarbonate, brine, then dried over magnesium sulfate and concentrated to give 20.5 g (98% yield) of Intermediate 2-1 which was used as is in the next step.

Intermediate 2-2

embedded image

29.2 g (125 mmol) of Intermediate 2-1 and 13.55 g (125 mmol) of anisole were dissolved in 440 mL dichloromethane and cooled to 0° C. 18.75 g (138 mmol) of aluminum chloride were added portionwise over 5 min, then the reaction was stirred at approx. 5-10° C. for 3 h. The reaction was quenched with water, and extracted with dichloromethane. The organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/dichloromethane) to give 28.95 g (72% yield) of Intermediate 2-2 as a colourless oil.

1H NMR (300 MHz, DMSO-d6) δ 7.58-7.42 (m, 2H), 7.31-7.18 (m, 1H), 7.00-6.93 (m, 2H), 6.85-6.76 (m, 2H), 3.71 (s, 3H), 1.69 (s, 6H).

Intermediate 2-3

embedded image

12.55 g (44.9 mmol) of 3,6-di-tert-butyl-9H-carbazole and 15.61 g (44.9 mmol) of Intermediate 2-2 were suspended in 449 mL DMF. 29.3 g (90 mmol) of caesium carbonate was added and the suspension was heated to 150° C. for 5 days. Then, the reaction was cooled to room temperature, quenched with water, and the resulting precipitate was filtered. The filtrate was extracted in dichloromethane 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/ethyl acetate) to give 16.8 g (64% yield) of Intermediate 2-3 as a viscous oil. The molecular mass of the product was confirmed by LC-MS [M+H] 582.2.

Intermediate 2-4

embedded image

13.51 g (23.19 mmol) of Intermediate 2-3 was dissolved in 184 mL dichloromethane, then cooled to 5° C. 24 mL (24 mmol) of boron tribromide (1.0 M in dichloromethane) was added dropwise, then the reaction was allowed to warm up to room temperature where it was stirred for 15 h. The reaction was cooled to 0° C. and quenched with saturated sodium bicarbonate solution, followed by extraction with dichloromethane 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/ethyl acetate) to give a white solid, which was further precipitated from dichloromethane/ethanol to give 8.65 g (65% yield) of Intermediate 2-4 as a white solid. The molecular mass of the product was confirmed by LC-MS [M+H] 568.6.

Intermediate 2-5

embedded image

8.64 g (15.2 mmol) of Intermediate 2-4 was dissolved in 76 mL dichloromethane, then cooled to 0° C. 5.29 mL (38 mmol) of triethylamine was added to the solution, followed by the dropwise addition of 4.7 mL (27.8 mmol) of triflic anhydride to give a dark, smoky solution. Then, the reaction was allowed to warm up to room temperature, where it was stirred for 2.5 h. Then, the reaction was quenched by the addition of water, then extracted with dichloromethane 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was precipitated from dichloromethane/ethanol to give 9.47 g (89% yield) of Intermediate 2-5 as a beige solid. The molecular mass of the product was confirmed by LC-MS [M+H] 700.2.

Intermediate 2-6

embedded image

A solution of 3.03 g (13.28 mmol) of 2-bromo-5-(tert-butyl)aniline in 24 mL tetrahydrofuran was cooled to −78° C., and 9.13 mL (14.61 mmol) of n-butyl lithium 1.6M in hexane was added dropwise. The reaction was stirred for 1.5 h, after which 7.71 mL (33.2 mmol) triisopropyl borate were added. Then, reaction was allowed to warm up to room temperature, where it was stirred for 15 h. The reaction was quenched with 1 M hydrochloric acid solution, and extracted with ethyl acetate 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum to give 2.5 g (98%) of Intermediate 2-6 which was used as is for the next step.

Intermediate 2-7

embedded image

5.09 g (7.26 mmol) of Intermediate 2-5, 2.45 g (8.89 mmol) of Intermediate 2-6, 2.51 g (18.15 mmol) of potassium carbonate were suspended in a mixture of 100 mL dioxane and 25 mL water. The mixture was evacuated and backfilled with argon 4 times. 0.21 g (0.18 mmol) of palladium tetrakis (tetrakis(triphenylphosphine)palladium(0)) were added, and the reaction was stirred at 70° C. for 14 h. The reaction was diluted with ethyl acetate/water, and the layers were separated. The organic layer was extracted with ethyl acetate 2 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/ethyl acetate) to give 4.24 g (83%) of Intermediate 2-7 as a white solid. The molecular mass of the product was confirmed by LC-MS [M+H] 701.7.

Intermediate 2-8

embedded image

6.57 g (9.39 mmol) of Intermediate 2-7 was dissolved in 94 mL dichloroethane and cooled to 0° C. 12.15 g (70.4 mmol) of meta-chloroperbenzoic acid were added to the reaction, then allowed to warm up to room temperature where it was stirred for 15 h. The reaction was quenched by the addition of 1 N sodium hydroxide, and extracted in dichloromethane 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/ethyl acetate) to give 2.1 g (31%) of Intermediate 2-8 as a white solid. The molecular mass of the product was confirmed by LC-MS [M+H] 729.7.

Intermediate 2-9

embedded image

2.1 g (2.88 mmol) of Intermediate 2-8 and 11.44 g (43.2 mmol) of triphenylphosphine were dissolved in 25 mL of ortho-dichlorobenzene and heated to 180° C. for 3 days. The reaction was cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was washed with methanol several times, then the solid was purified by column chromatography (heptane/ethyl acetate) to give 1.65 g (83%) of Intermediate 2-9 as a white solid. The molecular mass of the product was confirmed by LC-MS [M+H] 775.6.

Intermediate 2-10

embedded image

1.38 g (1.98 mmol) of Intermediate 2-9, 0.55 g (2.11 mmol) of 1-(tert-butyl)-4-iodobenzene, and 0.5 g (5.20 mmol) of sodium tert-butoxide were suspended in 20 mL toluene. The mixture was evacuated and backfilled with argon 4 times. 45 mg (0.049 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 58 mg (0.099 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene were added and the mixture was bubbled with argon for 5 min, then heated to 115° C. for 15 h. The reaction was cooled to room temperature, quenched with water, and extracted with ethyl acetate 3 times. The combined organic layer was washed with brine, then dried over magnesium sulfate and concentrated under vacuum. The crude product was purified by column chromatography (heptane/dichloromethane) to give 1.15 g (70%) of Intermediate 2-10 as a white solid. The molecular mass of the product was confirmed by LC-MS [M+H] 831.7.

Compound 2

embedded image

1.1 g (1.32 mmol) of Intermediate 2-10 was dissolved in 35 mL tert-butylbenzene and argon was bubbled for 15 min, then cooled to 0° C. 1.4 mL (2.66 mmol) of tert-butyllithium (1.9 M in pentane) was added dropwise to the reaction, then the reaction was warmed up to room temperature where it was stirred for 1 h. The yellowish solution was cooled down to −30° C. and 0.25 ml (2.65 mmol) of tribromoborane were added. The reaction mixture was warmed up to room temperature, stirred for 1 h and then cooled down to 0° C. 0.5 ml (2.86 mmol) of N,N-diisopropylethylamine were added and the reaction mixture was heated to 165° C. for 2 h. 1.16 ml (6.63 mmol) of N,N-diisopropylethylamine were added again and the reaction mixture was heated to 165° C. for another 18 hours. The yellow suspension was cooled down to room temperature, quenched with 10% aqueous sodium acetate solution and extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated under vacuum. The isolated solid was purified by precipitation from acetonitrile, then from dichloromethane/petroleum ether to give 0.61 g (61% yield) of Compound 2 as a yellow solid. The molecular mass of the product was confirmed by LC-MS [M+H] 759.9.

EVALUATION OF COMPOUNDS

Next, the properties of the compounds used in the examples were measured. Measurement and calculation methods are shown below.

1.1 Photoluminescence Application Data

The toluene solutions of the compounds mentioned in the tables were prepared by dissolving the corresponding compound in toluene with a concentration of 10⁻⁶mol/L. The total fluorescence spectrum was measured in toluene solution using a FP-8300 JASCO Spectrofluorometer.

The photoluminescence (PL) data of inventive compound 1 in toluene solution has been determined and is summarized in the following table.

Compound
PL [nm]¹⁾
FWHM [nm]²⁾
PLQY [%]³⁾

Compound 1
447
26
92

¹⁾Photoluminescence

²⁾Full width at half maximum

³⁾Photoluminescence quantum yield

These results demonstrate that the inventive compounds give a narrow spectrum (small FWHM), i.e. good color purity.

embedded image

The photoluminescence (PL) data of inventive compound 2 and comparative compound 1 in toluene solution have been determined and are summarized in the following table.

Compound
PL [nm]¹⁾
FWHM [nm]²⁾
PLQY [%]³⁾

Compound 2
447
24
90

Comparative Compound 1
439
29
92

⁴⁾Photoluminescence

⁵⁾Full width at half maximum

⁶⁾Photoluminescence quantum yield

These results demonstrate that the inventive compounds give a narrow spectrum (small FWHM), i.e. good color purity.

embedded image

1.2 Device Application Data (Invented Compound as Emitter Dopant)
Preparation and Evaluation of Organic EL Devices

The organic EL devices were prepared and evaluated as follows:

Application Example 1

A glass substrate with 130 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first treated with N₂plasma for 100 sec. This treatment also improved the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.01-2 Å/sec at about 10⁻⁶-10⁻⁸mbar. As a hole injection layer, 10 nm-thick mixture of Compound HT-1 and 3% by weight of compound HI was applied. Then 80 nm-thick of compound HT-1 and 10 nm of Compound HT-2 were applied as hole-transporting layer 1 and hole-transporting layer 2, respectively. Subsequently, a mixture of 2% by weight of an emitter Compound 1 and 98% by weight of host Compound BH-1 was applied to form a 25 nm-thick fluorescent emitting layer. On the emitting layer, 10 nm-thick Compound ET-1 was applied as electron-transporting layer land 15 nm of Compound ET-2 as electron-transporting layer 2. Finally, 1 nm-thick LiF was deposited as an electron-injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. To characterize the OLED, electroluminescence (EL) spectra were recorded at various currents and voltages. EL peak maximum and Full Width at Half Maximum (FWHM) were recorded at 10 mA/cm². In addition, the current-voltage characteristic were measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage (Voltage) was given at a current density of 10 mA/cm².

The device results are shown in Table 1.

embedded image

TABLE 1

Appl. Ex.
Voltage, V
EQE, %
EL max, nm
FWHM, nm

Appl. Ex. 1
3.6
9.2
453
25

These results demonstrate that the compounds of the present invention give good EQE and narrow spectrum (small FWHM), i.e. good color purity when used as fluorescent emitting material in OLED.

Application Example 2

Application Example 1 was repeated except the emitter Compound 1 was replaced with compound 2 in fluorescent emitting layer. The device results are shown in Table 2.

Comparative Application Example 1 Application Example 1 was repeated except the emitter compound 1 was replaced with comparative compound 1 in fluorescent emitting layer. The device results are shown in Table 2.

TABLE 2

Appl. Ex.
Voltage, V
EQE, %
EL max, nm
FWHM, nm

Appl. Ex. 2
3.6
10.0
453
25

Comp. Appl. Ex. 1
3.6
6.2
446
33

These results demonstrate that the compounds of the present invention give good EQE and narrow spectrum (small FWHM), i.e. good color purity when used as fluorescent emitting material in OLED.

HETEROCYCLIC COMPOUND AND AN ORGANIC ELECTROLUMINESCENCE DEVICE COMPRISING THE HETEROCYCLIC COMPOUND

Information

Publication Number

Date Filed

Date Published

Inventors

Original Assignees

CPC

International Classifications

Abstract

Description

Claims

Priority Claims (1)

PCT Information