WO2018043241A1 - 有機発光素子ならびにそれに用いる発光材料および化合物 - Google Patents

有機発光素子ならびにそれに用いる発光材料および化合物 Download PDF

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WO2018043241A1
WO2018043241A1 PCT/JP2017/030115 JP2017030115W WO2018043241A1 WO 2018043241 A1 WO2018043241 A1 WO 2018043241A1 JP 2017030115 W JP2017030115 W JP 2017030115W WO 2018043241 A1 WO2018043241 A1 WO 2018043241A1
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substituted
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French (fr)
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一 中野谷
大貴 野田
安達　千波矢
桃香 宮島
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国立大学法人九州大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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  • the present invention relates to an organic light emitting device having high luminous efficiency.
  • the present invention also relates to a light emitting material and a compound used for the organic light emitting element.
  • organic light emitting devices such as organic electroluminescence devices (organic EL devices)
  • organic electroluminescence devices organic electroluminescence devices
  • various efforts have been made to increase the light emission efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials, and the like constituting the organic electroluminescence element.
  • studies on organic electroluminescence devices using compounds having a substituted or unsubstituted diarylboryl group as an acceptor group can also be found.
  • Patent Document 1 describes a compound having one substituted diarylboryl group.
  • Patent Document 1 describes a compound having one substituted diarylboryl group.
  • the present inventors actually evaluated the light emission characteristics of this compound, it has been found that the light emission efficiency is not sufficiently satisfactory, and it is necessary to provide a light emitting material having better light emission characteristics. did.
  • a compound having a structure represented by the following general formula (1) [1] A compound having a structure represented by the following general formula (1).
  • General formula (1) (D) m-Ar- (A) n
  • Ar represents an aromatic ring
  • D represents a substituent in which Hammett's ⁇ p is negative
  • A represents a substituent in which Hammett's ⁇ p is positive.
  • m and n each independently represents an integer of 2 or more, but m + n does not exceed the maximum number of substituents that can be substituted on the aromatic ring of Ar.
  • At least two of A are substituted or unsubstituted diarylboryl groups.
  • At least one of R 1 to R 5 independently represents a substituted or unsubstituted diarylboryl group, and at least two of R 1 to R 5 each independently represents a substituent having a negative Hammett ⁇ p, R 1 to R 5 each independently represents a hydrogen atom or a substituent having Hammett's ⁇ p of 0 or more.
  • R 1 or R 3 in the general formula (2) is a substituted or unsubstituted diarylboryl group.
  • R 3 in the general formula (2) is a substituted or unsubstituted diarylboryl group.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 And R 20 may be bonded to each other to form a cyclic structure.
  • R 11 , R 13 , R 15 , R 16 , R 18 and R 20 in the general formula (10) are alkyl groups.
  • the organic light-emitting device according to [21] comprising a light-emitting layer containing the compound according to any one of [1] to [19] on a substrate.
  • the compound of the present invention has high luminous efficiency. For this reason, the compound of this invention is useful as a luminescent material, and the organic light emitting element which has the outstanding luminescent property is realizable by using it as a luminescent material of an organic light emitting element. Moreover, since the compound of this invention can radiate
  • 2 is a transient decay curve of emission intensity of a toluene solution of Compound 1. It is the transient decay curve of the emitted light intensity measured at the temperature of 5K, 100K, 200K, and 300K about the mCBP co-evaporated thin film of the compound 1 (the density
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the compound of the present invention has a structure represented by the following general formula (1). Moreover, the luminescent material of the present invention is characterized by containing a compound represented by the following general formula (1). Furthermore, the organic light-emitting device of the present invention is characterized by containing a compound represented by the following general formula (1). Therefore, first, the compound represented by the general formula (1) will be described.
  • Ar represents an aromatic ring.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring.
  • the aromatic ring may be a monocyclic aromatic ring or an aromatic ring having a condensed polycyclic structure or a ring assembly structure.
  • the aromatic hydrocarbon ring preferably has 6 to 40 carbon atoms, and more preferably a condensed ring having a structure in which a benzene ring or a plurality of benzene rings are condensed.
  • aromatic hydrocarbon ring examples include a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring, triphenylene ring, pyrene ring, chrysene ring, tetracene ring, pentacene ring, coronene ring, and the like.
  • a naphthalene ring is preferable, and a benzene ring is more preferable.
  • the heteroatom in the aromatic heterocycle is preferably at least one of N, O, and S.
  • the aromatic heterocycle preferably has 3 to 40 carbon atoms, more preferably a condensed ring having a structure in which a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring are condensed. More preferably, it is a 5-membered ring.
  • aromatic heterocycle examples include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine A ring etc.
  • a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, and a furazane ring are preferable.
  • the aromatic ring represented by Ar may contain a spiro atom.
  • it may include a spiro ring in which a plurality of rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic hetero ring are bonded via a spiro atom, and spirobifluorene can be exemplified. .
  • An aromatic ring containing such a spiro atom is also preferred.
  • D represents a substituent in which Hammett's ⁇ p is negative
  • A represents a substituent in which Hammett's ⁇ p is positive
  • Hammett's ⁇ p is L. P. It was proposed by Hammett and quantifies the effect of substituents on the acid dissociation equilibrium of para-substituted benzoic acids.
  • a Hammett ⁇ p being a positive value means that the substituent is an acceptor group (electron-withdrawing group), and a Hammett ⁇ p being a negative value means that the substituent is a substituent.
  • the substituent represented by A preferably has a Hammett's ⁇ p of 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.
  • a substituent of 0.5 or more can be selected, or a substituent of 0.7 or more can be selected.
  • the substituent represented by D preferably has a Hammett's ⁇ p of ⁇ 0.1 or less, more preferably ⁇ 0.2 or less, and even more preferably ⁇ 0.3 or less.
  • a substituent of ⁇ 0.5 or less can be selected, or a substituent of ⁇ 0.7 or less can be selected.
  • m and n each independently represent an integer of 2 or more, but m + n does not exceed the maximum number of substituents that can be substituted on the aromatic ring of Ar.
  • m represents the number of substitutions of D substituted on the aromatic ring
  • n represents the number of substitutions of A substituted on the aromatic ring. That is, the compound represented by the general formula (1) of the present invention has two or more D and A in the molecule. Several D may mutually be same or different, and several A may mutually be same or different.
  • the group capable of substituting a substituent in an aromatic ring include a methine group (—CH ⁇ ) constituting an aromatic hydrocarbon ring and an aromatic heterocycle, and an imino group (— NH-) and the like.
  • a methine group —CH ⁇
  • an imino group — NH-
  • Ar is a benzene ring
  • the maximum number of substituents that can be substituted is 6, and m + n does not exceed 6.
  • the substitution position of D and A in the aromatic ring is not particularly limited.
  • Ds when two Ds are bonded to the benzene ring, it is preferably bonded to a position where they are para to each other.
  • A it is preferable that they are bonded at positions that are para positions to each other.
  • the compound represented by the general formula (1) becomes a radical, a resonance structure can be taken, and the radical is stabilized. As a result, an excited state can be efficiently generated from radicals.
  • the aromatic ring represented by Ar is a condensed ring, a plurality of D may be bonded to the same ring or may be bonded to different rings, and a plurality of A may be bonded to the same ring.
  • At least two of A are substituted or unsubstituted diarylboryl groups.
  • a plurality of substituted or unsubstituted diarylboryl groups may be the same or different from each other, but are preferably the same.
  • two A's are both substituted or unsubstituted diarylboryl groups.
  • n is 3 or more, among the plurality of A, two or more diarylboryl groups may be present, or three or more. In other words, when n is 3 or more, all of A may be a substituted or unsubstituted diarylboryl group, or a part of A may be a substituted or unsubstituted diarylboryl group.
  • all of the plurality of A are substituted or unsubstituted diarylboryl groups. That is, all the substituents (A) having a positive Hammett ⁇ p present in the molecule of the compound represented by the general formula (1) are preferably “substituted or unsubstituted diarylboryl groups”.
  • the “substituted or unsubstituted diarylboryl group” means that two hydrogen atoms bonded to a boron atom of a boryl group (—BH 2 ) are substituted or unsubstituted aryl groups or substituted or unsubstituted hetero groups, respectively.
  • the aryl group in the substituted or unsubstituted aryl group is a monovalent aromatic hydrocarbon group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring constituting the aryl group the preferred range and specific examples of the aromatic hydrocarbon ring in Ar can be referred to.
  • the heteroaryl group in the substituted or unsubstituted heteroaryl group is a monovalent aromatic heterocyclic group obtained by removing one hydrogen atom from an aromatic heterocyclic ring.
  • the two groups bonded to the boron atom (B) of the diarylboryl group may be the same or different from each other, but are preferably the same. Further, the two groups bonded to the boron atom (B) of the diarylboryl group may both be substituted or unsubstituted aryl groups, or both may be substituted or unsubstituted heteroaryl groups.
  • One may be a substituted or unsubstituted aryl group, and the other may be a substituted or unsubstituted heteroaryl group.
  • the two groups bonded to the boron atom (B) of the diarylboryl group are preferably both substituted or unsubstituted aryl groups.
  • the substituted or unsubstituted aryl group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and more preferably a substituted or unsubstituted phenyl group.
  • substituents that can be substituted on the aryl group and heteroaryl group refer to preferred ranges and specific examples of substituents that can be taken by R 11 to R 20 in the following general formula (10). it can.
  • the substituent which substitutes to an aryl group and heteroaryl group may couple
  • specific examples of the cyclic structure formed by bonding the substituent to the adjacent substituent specific examples of the cyclic structure formed by bonding R 11 and R 12 to each other can be referred to.
  • the substituted or unsubstituted diarylboryl group preferably has a structure represented by the following general formula (10).
  • R 11 to R 20 each independently represents a hydrogen atom or a substituent.
  • the number of substituents is not particularly limited, and all of R 11 to R 20 may be unsubstituted (that is, hydrogen atoms).
  • the substitution position and the number of substitutions when the group represented by the general formula (10) has a substituent are not particularly limited, but the number of substitutions is preferably 0 to 6. When having a plurality of substituents, they may be the same or different from each other, but are preferably the same.
  • the group represented by the general formula (12) has a substituent, it is preferably at least one of R 11 to R 14 and at least one of R 17 to R 20 .
  • R 11 , R 13 , R 15 , R 16 , R 18 and R 20 are substituents can be preferably exemplified.
  • R 11 to R 20 in the general formula (10) can take include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 alkylthio groups, alkyl substituted amino groups having 1 to 20 carbon atoms, acyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 40 carbon atoms, heteroaryl groups having 3 to 40 carbon atoms, and 12 to 40 carbon atoms Diarylamino group, substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, 1 to 1 carbon atoms 10 alkylsulfonyl groups, haloalkyl groups having 1 to 10 carbon atoms, amide
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted diarylamino group having 12 to 40 carbon atoms, and a substituted or unsubstituted carbazolyl group having 12 to 40 carbon atoms.
  • substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 1 to 10 carbon atoms.
  • an unsubstituted dialkylamino group a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms, and particularly preferred substituents having 1 to 10 carbon atoms.
  • the alkyl group in the present specification may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, and butyl. Group, t-butyl group, pentyl group, hexyl group and isopropyl group.
  • the aryl group may be a single ring or a fused ring, and specific examples thereof include a phenyl group and a naphthyl group.
  • the alkoxy group may be linear, branched or cyclic, and more preferably has 1 to 6 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group. Group, pentyloxy group, hexyloxy group, isopropoxy group.
  • the two alkyl groups of the dialkylamino group may be the same or different from each other, but are preferably the same.
  • the two alkyl groups of the dialkylamino group may each independently be linear, branched or cyclic, and more preferably have 1 to 6 carbon atoms.
  • Specific examples include a methyl group, an ethyl group, Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.
  • the aryl group may be a single ring or a fused ring, and specific examples thereof include a phenyl group and a naphthyl group.
  • the heteroaryl group may be a monocyclic ring or a fused ring, and specific examples thereof include pyridyl group, pyridazyl group, pyrimidyl group, triazyl group, triazolyl group, benzotriazolyl group, and carbazolyl group. These heteroaryl groups may be a group bonded through a hetero atom or a group bonded through a carbon atom constituting a heteroaryl ring.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 And R 20 may be bonded to each other to form a cyclic structure, or preferably bonded to each other to form no cyclic structure.
  • the cyclic structure may be an aromatic ring or an aliphatic ring, may contain a hetero atom, and the cyclic structure is a condensed ring of two or more rings. There may be.
  • the hetero atom herein is preferably selected from the group consisting of N, O and S.
  • R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 16 and R 17 , R 17 and R 18 , R 18 and R 19 , R 19 and R 20 are bonded to each other
  • Examples of the cyclic structure formed as follows are benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, Examples include a thiazole ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and
  • each benzene ring bonded to the boron atom B of the general formula (10) is a monocyclic benzene ring, or another benzene ring is condensed with the benzene ring to form a naphthalene ring.
  • the cyclic structure R 15 and R 16 is formed by bonding, with 5-membered ring R 15 and R 16 form constitutes a single bond, R 15 and R 16 constitute a methylene group Examples thereof include a 6-membered ring to be formed.
  • the methylene group may be substituted with an alkyl group or an aryl group.
  • a substituent having a positive Hammett ⁇ p that can be taken by the remaining A is not particularly limited. Examples thereof include a halogen atom, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a phenyl group, a cyano group, a pyrimidine group, a triazine group, and a trifluoro group.
  • the remaining A is 2 or more, the Hammett ⁇ p positive substituents represented by them may be the same or different.
  • the substituent having a negative Hammett ⁇ p represented by D is not particularly limited, and examples thereof include a substituted amino group, an alkoxy group, and an alkyl group.
  • examples of the substituent of the substituted amino group include an aryl group having 6 to 40 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and the like. May be bonded to each other to form a heteroaryl group.
  • Preferred examples of the substituted amino group and heteroaryl group as a substituent having a negative Hammett ⁇ p represented by D include groups represented by the following general formulas (11) to (14). The group represented by (11) is more preferable.
  • R 21 to R 28 , R 41 to R 46 , R 51 to R 62 and R 71 to R 80 each independently represents a hydrogen atom or a substituent.
  • R 75 and R 76 may be bonded to each other to form a cyclic structure.
  • the substitution position and the number of substitutions when the groups represented by the general formulas (11) to (14) have a substituent are not particularly limited.
  • the number of substitutions for each group is preferably 0 to 6, more preferably 0 to 4, for example, 0 to 2 is also preferable. When having a plurality of substituents, they may be the same or different from each other, but are preferably the same.
  • any of R 21 , R 23 , R 26 and R 28 is preferably a substituent.
  • R 21 and R 28 are substituents, R 23 and R 26 are substituents, and R 21 , R 23 , R 26 , and R 28 are all substituents. it can.
  • R 21 to R 28 are preferably all hydrogen atoms, R 22 and R 27 are trifluoromethyl groups, and R 21 , R 23 to R 26 , It is also preferred that each R 28 is independently a hydrogen atom or a substituent.
  • R 22 and R 27 are trifluoromethyl groups and R 21 , R 23 to R 26 and R 28 are each independently a hydrogen atom or a substituent
  • R 21 , R 23 to R 26 and R 28 have a substituent
  • any of them may be a substituent
  • the number of substituents is not particularly limited.
  • the number of substituents in R 21 , R 23 to R 26 and R 28 is preferably 0 to 4, more preferably 0 to 2, for example, 0.
  • the two or more substituents may be the same or different, but may be the same. preferable.
  • R 21 , R 23 to R 26 , and R 28 have a substituent
  • at least one of R 23 to R 26 is preferably a substituent.
  • R 23 and R 26 are substituents
  • the case where R 24 and R 25 are substituents can be preferably exemplified, and it is particularly preferable that R 23 and R 26 are substituents.
  • R 23 and R 26 are substituents, the oxidation resistance of the compound tends to be improved. By protecting the 3- and 6-positions of the carbazol-9-yl group with a substituent to make it less susceptible to oxidation, it is presumed that dimerization of the compound is suppressed and stability is improved.
  • the substituent represented by R 23 and R 26 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group or a tert-butyl group. Is more preferable.
  • At least one of R 21 , R 23 to R 26 and R 28 is preferably a carbazolyl group, more preferably a carbazol-2-yl group, a carbazol-3-yl group, or a carbazol-9-yl group. .
  • the HOMO level and the LUMO level of the compound represented by the general formula (1) can be further lowered.
  • the carbazolyl group may be unsubstituted or substituted with a substituent, but is substituted with a cyano group It is preferable.
  • the substitution position of the cyano group is at least one of the 6-position and the 8-position in the carbazol-2-yl group.
  • the carbazol-3-yl group is preferably in the 7-position
  • the carbazol-9-yl group is preferably in at least one of the 2-position and the 7-position.
  • the carbazolyl group represented by at least one of R 21 , R 23 to R 26 and R 28 is a carbazol-2-yl group in which at least one of the 6-position and the 8-position is substituted with a cyano group. More preferred.
  • the carbazolyl group represented by R 21 , R 23 to R 26 and R 28 is preferably substituted when the 3-position, 6-position and 9-position can be substituted, and the substituent has 1 to 20 carbon atoms.
  • An alkyl group and an aryl group having 6 to 40 carbon atoms are more preferable, and an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 15 carbon atoms are more preferable. If the 3-position, 6-position and 9-position are substituted, oxidation is difficult and dimerization can be suppressed, which is preferable in terms of stability.
  • carbazolyl group among R 21, R 23 ⁇ R 26 , R 28 is preferably at least one of R 23 ⁇ R 26, and more preferably R 23 and R 26.
  • the number of carbazole rings present in the molecule of the compound represented by the general formula (1) is preferably 4 or less.
  • any of R 42 to R 46 is preferably a substituent.
  • R 42 is a substituent and a case where R 43 is a substituent can be preferably exemplified.
  • any of R 52 to R 60 is preferably a substituent.
  • any of R 52 to R 54 is a substituent and a case where any of R 55 to R 60 is a substituent can be preferably exemplified.
  • any of R 72 to R 74 and R 77 to R 79 is preferably a substituent.
  • R 72 and R 79 are substituents
  • R 73 and R 78 are substituents
  • R 74 and R 77 are substituents
  • R 72 , R 74 , R 77 and R 79 are The case where it is a substituent can be illustrated preferably.
  • R 74 and R 77 are substituents
  • the case where R 72 , R 74 , R 77 and R 79 are substituents can be exemplified more preferably.
  • the substituents at this time are particularly preferably each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and preferably has 1 to 6 carbon atoms. And more preferably an unsubstituted alkyl group, an unsubstituted aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms substituted with an aryl group having 6 to 10 carbon atoms.
  • R 75 and R 76 are preferably hydrogen atoms, and preferably bonded to each other to form a cyclic structure.
  • R 75 and R 76 constitute an oxy group (—O—), a sulfide group (—S—) or a methylene group (—CH 2 —). And a 6-membered ring formed as described above.
  • the skeleton structure of the group represented by the general formula (14) is a phenoxazine skeleton, a phenothiazine skeleton, or a dihydroacridine skeleton.
  • the methylene group may be substituted with an alkyl group or an aryl group.
  • R 10 to R 20 in the general formula (10) the preferred ranges and specific examples of the substituents that can be taken by R 10 to R 20 in the general formula (10) can be referred to.
  • an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms are preferable.
  • the aromatic ring represented by Ar in the general formula (1) may be substituted with a substituent other than the groups shown as the substituents represented by D and A in the above.
  • substituent that can be substituted on the aromatic ring preferred substituents that can be taken by the following R 1 to R 5 can be referred to.
  • the substituent having a negative Hammett ⁇ p corresponds to the substituent represented by D
  • the substituent having a positive Hammett ⁇ p corresponds to the substituent represented by A.
  • the aromatic ring represented by Ar may be substituted with a substituent having Hammett's ⁇ p of 0.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
  • a 1 represents a substituted or unsubstituted diarylboryl group
  • at least one of R 1 to R 5 independently represents a substituted or unsubstituted diarylboryl group.
  • R 1 to R 5 independently represents a substituted or unsubstituted diarylboryl group.
  • the substituted or unsubstituted diarylboryl groups represented by at least one of A 1 and R 1 to R 5 may be the same or different from each other, but are preferably the same.
  • any one of R 1 to R 5 is a substituted or unsubstituted diarylboryl group
  • any of R 1 to R 3 may be used.
  • a combination of R 1 and R 3 or a combination of R 2 and R 4 can be exemplified.
  • combinations of R 1 , R 3 and R 4 can be exemplified.
  • R 1 to R 5 each independently represent a substituent having a negative Hammett ⁇ p.
  • the substituent having a negative Hammett ⁇ p is preferably a group represented by the general formulas (11) to (14), and more preferably a group represented by the general formula (11).
  • the substituents having negative Hammett ⁇ p represented by at least two of R 1 to R 5 may be the same or different from each other, but are preferably the same.
  • R 1 to R 5 When any two of R 1 to R 5 are substituents having negative Hammett ⁇ p, a combination of R 1 and R 2, a combination of R 2 and R 3, a combination of R 3 and R 4 , R 1 and the combination of R 3, the combination of R 2 and R 4, can be exemplified a combination of R 1 and R 4 or the like, although any three, if Hammett ⁇ p is a negative substituent, and R 1 A combination of R 3 and R 4 can be exemplified. When any four of them are a substituent in which Hammett's ⁇ p is negative, a combination of R 1 , R 3 , R 4 and R 5 and a combination of R 1 , R 2 , R 4 and R 5 may be exemplified.
  • a combination of R 2 and R 3, a combination of R 3 and R 4 , or a combination of R 1 and R 4 is preferred when Hammett ⁇ p is a negative substituent
  • Preferred is when the combination of R 1 and R 4 is a substituent having a negative Hammett ⁇ p.
  • the resonance structure can be formed when the compound represented by the general formula (2) becomes a radical, and the radical is stable. Turn into. As a result, an excited state can be efficiently generated from radicals.
  • R 1 ⁇ R 5 represents a substituted or unsubstituted Jiariruboriru group
  • at least two Hammett's ⁇ p of R 1 ⁇ R 5 represent a negative substituent
  • the rest of R 1 to R 5 each independently represents a hydrogen atom or a substituent having Hammett's ⁇ p of 0 or more.
  • a specific example of a substituent having a Hammett ⁇ p greater than 0 represented by the remainder of R 1 to R 5 that is, a substituent having a positive Hammett ⁇ p is represented by one of a plurality of A in the general formula (1).
  • R 1 ⁇ R 5 in the general formula (2) may take the substituent other than the group shown as a substituent represented by R 1 ⁇ R 5 above.
  • substituents which R 1 to R 5 can take are exemplified.
  • Substituents represented by R 1 ⁇ R 5 represents at least one substituted or unsubstituted Jiariruboriru group R 1 ⁇ R 5, at least two Hammett's ⁇ p of R 1 ⁇ R 5 represent a negative substituent
  • the Hammett ⁇ p may be a negative substituent
  • the Hammett ⁇ p may be a positive substituent
  • the Hammett ⁇ p may be a substituent of 0.
  • R 1 to R 5 can take include, for example, a hydroxy group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 1 carbon atom.
  • substituents that can be substituted with a substituent may be further substituted. More preferred substituents are a hydroxy group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted group having 1 to 20 carbon atoms.
  • substituents are a hydroxy group, a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 1 to 10 carbon atoms.
  • R 1 to R 5 are two or less hydrogen atoms, preferably two, and preferably zero.
  • R 3 is a substituted or unsubstituted diarylboryl group
  • at least one of R 1 and R 2 and at least one of R 4 and R 5 are Hammett's ⁇ p is a negative substituent Can be mentioned.
  • R 3 is a substituted or unsubstituted diarylboryl group
  • one of R 1 and R 2 and one of R 4 and R 5 are Hammett's ⁇ p negative substituent Can be mentioned.
  • Further preferred combinations include, for example, the case where R 3 is a substituted or unsubstituted diarylboryl group, and R 1 and R 4 are Hammett's ⁇ p is a negative substituent.
  • R 1 in the general formula (1) is a substituted or unsubstituted diarylboryl group, and at least two of R 2 to R 5 are Hammett's ⁇ p is a negative substituent.
  • R 1 in the general formula (1) is a substituted or unsubstituted diarylboryl group, and R 3 and R 4 are Hammett's ⁇ p is a negative substituent.
  • the substitution position and the number of substitutions, and the group represented by the general formula (11) The bonding site to the benzene ring, the substitution position and the number of substitutions of the carbazolyl group introduced into the group represented by the general formula (11), the bonding site to the group represented by the general formula (11) in the carbazolyl group, etc.
  • the symmetry and linearity of the molecular structure can be controlled. For example, if the symmetry of the molecule is high, there is an advantage that the electron transition property becomes high. On the other hand, it is preferable that the molecule is linear because polarization is increased and the quantum yield is increased, but the electron transition property is lowered.
  • the molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, more preferably 1000 or less, and even more preferably 800 or less. The lower limit of the molecular weight is usually 247 or more, preferably 290 or more.
  • the compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.
  • a compound containing a plurality of structures represented by the general formula (1) in the molecule for the light emitting layer of the organic light emitting device.
  • a polymer obtained by polymerizing a polymerizable monomer having a structure represented by the general formula (1) for a light emitting layer of an organic light emitting device Specifically, by preparing a monomer having a polymerizable functional group in any one of Ar, D, and A in the general formula (1) and polymerizing it alone or copolymerizing with other monomers, It is considered that a polymer having a repeating unit is obtained and the polymer is used for a light emitting layer of an organic light emitting device.
  • dimers and trimers are obtained by coupling compounds having a structure represented by the general formula (1) and used in the light emitting layer of the organic light emitting device.
  • any one of Ar, D, and A in the general formula (1) is represented by the following general formula (15) or (16). The thing which has a structure represented can be mentioned.
  • L 1 and L 2 each represent a linking group.
  • the linking group preferably has 0 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 2 to 10 carbon atoms. And preferably has a structure represented by - linking group -X 11 -L 11.
  • X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 11 represents a linking group, and is preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
  • R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
  • it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms.
  • An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
  • the structure of the repeating unit include those in which structures represented by the following formulas (21) to (24) are introduced into any of Ar, D, and A in the general formula (1).
  • the number of structures represented by the following formulas (21) to (24) introduced into any one of Ar, D, and A in the general formula (1) may be two or more, but it should be one. preferable.
  • the polymer having a repeating unit containing these formulas (21) to (24) is prepared by introducing a hydroxy group into at least one of Ar, D and A in the general formula (1) and using it as a linker. Can be synthesized by introducing a polymerizable group and polymerizing the polymerizable group.
  • the polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or other structures may be used. It may be a polymer containing repeating units.
  • the repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.
  • the compound represented by the above general formula (1) is a novel compound.
  • the method for synthesizing the compound represented by the general formula (1) is not particularly limited.
  • the synthesis of the compound represented by the general formula (1) can be performed by appropriately combining known synthesis methods and conditions.
  • the compound represented by the general formula (1) is a compound represented by the general formula (2)
  • R 3 is a group (diarylboryl group) represented by the general formula (10)
  • R 1 A compound in which R 4 is a group represented by the general formula (11) can be synthesized by two reactions represented by the following reaction formulas (I) and (II).
  • X 1 to X 3 represent a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X 1 and X 3 are preferably fluorine atoms, and X 2 is preferably a bromine atom.
  • the above reaction is an application of a known coupling reaction, and known reaction conditions can be appropriately selected and used. The details of the above reaction can be referred to the synthesis examples described below.
  • the compound represented by the general formula (1) can also be synthesized by combining other known synthesis reactions.
  • the compound represented by the general formula (1) of the present invention has high luminous efficiency.
  • the compound represented by the general formula (1) of the present invention has a structure in which a diarylboryl group is substituted on an aromatic ring in which Hammett ⁇ p is substituted with a negative substituent, and Hammett ⁇ p is negative.
  • the compound represented by the general formula (1) is useful as a light emitting material of an organic light emitting device, and can be effectively used as a light emitting material of a light emitting layer of the organic light emitting device.
  • the compound represented by the general formula (1) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence. That is, the present invention relates to a delayed phosphor having a structure represented by the general formula (1), an invention using a compound represented by the general formula (1) as a delayed phosphor, and a general formula (1).
  • An invention of a method for emitting delayed fluorescence using the represented compound is also provided.
  • An organic light emitting device using such a compound as a light emitting material emits delayed fluorescence and has a feature of high luminous efficiency. The principle will be described below by taking an organic electroluminescence element as an example.
  • the organic electroluminescence element carriers are injected into the light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light.
  • 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used.
  • the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high.
  • delayed fluorescent materials after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit fluorescence.
  • a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful.
  • excitons in the excited singlet state emit fluorescence as usual.
  • excitons in the excited triplet state absorb heat generated by the device and cross between the excited singlets to emit fluorescence.
  • the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised.
  • the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.
  • organic light-emitting devices such as an organic photoluminescence device (organic PL device) and an organic electroluminescence device (organic EL device) can be provided.
  • the organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode.
  • the organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer.
  • Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer.
  • the hole transport layer may be a hole injection / transport layer having a hole injection function
  • the electron transport layer may be an electron injection / transport layer having an electron injection function.
  • FIG. 1 A specific example of the structure of an organic electroluminescence element is shown in FIG. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode. Below, each member and each layer of an organic electroluminescent element are demonstrated. In addition, description of a board
  • the organic electroluminescence device of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements.
  • a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture
  • Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.
  • the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material.
  • a luminescent material the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used.
  • a host material in addition to the light emitting material in the light emitting layer.
  • the host material an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used.
  • singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted.
  • high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention.
  • the organic light emitting device or organic electroluminescent device of the present invention light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
  • the amount of the compound of the present invention, which is a light emitting material is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
  • the host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
  • the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission.
  • the injection layer can be provided as necessary.
  • the blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer.
  • the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
  • a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
  • the blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer.
  • the term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
  • the material for the hole blocking layer the material for the electron transport layer described later can be used as necessary.
  • the electron blocking layer has a function of transporting holes in a broad sense.
  • the electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .
  • the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  • the layer when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer.
  • a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided.
  • an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided.
  • the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the compound represented by the general formula (1) may be used not only for the light emitting layer but also for layers other than the light emitting layer.
  • the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different.
  • the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. .
  • the method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.
  • the preferable material which can be used for an organic electroluminescent element is illustrated concretely.
  • the material that can be used in the present invention is not limited to the following exemplary compounds.
  • R, R ′, and R 1 to R 10 each independently represent a hydrogen atom or a substituent.
  • X represents a carbon atom or a hetero atom forming a ring skeleton
  • n represents an integer of 3 to 5
  • Y represents a substituent
  • m represents an integer of 0 or more.
  • the organic electroluminescent device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
  • phosphorescence is hardly observable at room temperature in ordinary organic compounds such as the compounds of the present invention because the excited triplet energy is unstable and converted to heat, etc., and has a short lifetime and immediately deactivates.
  • the excited triplet energy of a normal organic compound it can be measured by observing light emission under extremely low temperature conditions.
  • the organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer.
  • the organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention.
  • organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
  • the features of the present invention will be described more specifically with reference to synthesis examples and examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
  • the HOMO level and LUMO level were measured using an atmospheric photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd .: AC3) and a UV / Vis / NIR spectrophotometer (manufactured by PerkinElmer: LAMBDA950).
  • Example 1 Compound 1 obtained in Synthesis Example 1 had a HOMO level of 6.06 eV and a LUMO level of 3.62 eV. Using this compound 1, a thin film was produced as follows. Compound 1 of toluene solution (concentration 10? 5 mol / L) was prepared in a glove box in an Ar atmosphere. In addition, a thin film (single film) of Compound 1 was formed to a thickness of 100 nm on a quartz substrate by a vacuum deposition method under conditions of a degree of vacuum of 1 ⁇ 10 4 Pa or less.
  • compound 1 and 3,3′-di (9H-carbazol-9-yl) -1,1 ′ are formed on a quartz substrate by a vacuum deposition method under the condition of a vacuum degree of 1 ⁇ 10 4 Pa or less.
  • -Biphenyl (mCBP) was deposited from a different deposition source, and a thin film (dope film) having a concentration of Compound 1 of 6% by weight was formed to a thickness of 100 nm.
  • FIG. 2 shows the results of measuring a transient attenuation curve of 555 nm emission by 325 nm excitation light after nitrogen bubbling was performed on the toluene solution of Compound 1.
  • the mCBP co-deposited thin film of Compound 1 (the concentration of Compound 1 is 6% by weight) was measured for a transient attenuation curve of 555 nm emission by 337 nm excitation light at temperatures of 5K, 100K, 200K, and 300K. Shown in In the transient decay curve of FIG. 3, the fluorescence lifetime was extended as the measurement conditions were increased, and it was thus confirmed that Compound 1 is a thermally activated delayed phosphor.
  • Example 2 A toluene solution of Compound 2 was prepared in the same manner as in Example 1 except that Compound 2 was used instead of Compound 1.
  • FIG. 4 shows the results of measuring a transient decay curve of 481 nm emission by 325 nm excitation light before and after nitrogen bubbling of the toluene solution of Compound 2.
  • the fluorescence component with a long light emission lifetime is recognized with the fluorescence component with a short light emission lifetime. From this, it was confirmed that the compound 2 is a delayed phosphor. Note that the emission lifetime is longer after nitrogen bubbling than before nitrogen bubbling.
  • quenching of triplet excitons by oxygen is suppressed and excited triplet state It is presumed that the reverse intersystem crossing from to the excited singlet state was promoted.
  • Comparative Example 1 A toluene solution of Comparative Compound 1 was prepared in the same manner as in Example 1 except that Comparative Compound 1 having the following structure was used instead of Compound 1 (Cz represents a carbazol-9-yl group).
  • Table 1 shows the results of measuring the photoluminescence quantum yield, delayed fluorescence lifetime, and emission maximum wavelength with 325 nm excitation light for each of the toluene solutions prepared in Examples 1 and 2 and Comparative Example 1.
  • the photoluminescence quantum yield was measured under two conditions: a state where the toluene solution was placed in the atmosphere and a state where the solution was deaerated.
  • the toluene solutions of compounds 1 and 2 each having two substituted diarylboryl groups and two carbazol-9-yl groups (donor groups) are obtained by replacing one substituted diarylboryl group with one carbazol-9-yl group 2 Compared with the toluene solution of Comparative Compound 1 having a light emitting property, it had a remarkably high luminous efficiency.
  • Example 3 Each thin film was laminated at a vacuum degree of 1 ⁇ 10 4 Pa or less by a vacuum deposition method on a glass substrate on which an anode made of indium tin oxide (ITO) having a thickness of 100 nm was formed.
  • ITO indium tin oxide
  • dipyrazino [2,3-f: 20,30-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) is formed to a thickness of 10 nm on a glass substrate
  • 4,4′-cyclohexylidenebis [N, N-bis (4-methylphenyl) benzenamine] (TAPC) is formed to a thickness of 30 nm
  • Compound 1 and mCBP are co-evaporated to form a film having a thickness of 30 nm.
  • concentration of Compound 1 was 6% by weight).
  • FIG. 5 shows the external quantum efficiency (EQE) -current density characteristics of the produced organic electroluminescence elements.
  • “6 wt%”, “15 wt%”, and “25 wt%” are organic electroluminescent elements in which the concentration of Compound 1 in the light emitting layer is 6 wt%, 15 wt%, and 25 wt%, respectively.
  • the maximum external quantum efficiency of each organic electroluminescence device is 18.3% when the concentration of Compound 1 is 6% by weight, 15.7% when the concentration of Compound 1 is 15% by weight, and the concentration of Compound 1 It was 13.9% with 25% by weight, and a very high luminous efficiency could be obtained.
  • the compound of the present invention has a very high luminous efficiency. For this reason, the compound of this invention is useful as a luminescent material for organic light emitting elements. Moreover, since the organic light emitting device of the present invention contains such a light emitting material, it can realize excellent light emitting characteristics. For this reason, this invention has high industrial applicability.

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