WO2007072691A1

WO2007072691A1 - ORGANIC BORON π-ELECTRON SYSTEM COMPOUND AND INTERMEDIATE FOR PRODUCTION OF THE COMPOUND

Info

Publication number: WO2007072691A1
Application number: PCT/JP2006/324467
Authority: WO
Inventors: Shigehiro Yamaguchi; Atsushi Wakamiya; Kenji Mori; Cui-Hua Zhao
Original assignee: National University Corporation Nagoya University
Priority date: 2005-12-16
Filing date: 2006-12-07
Publication date: 2007-06-28
Also published as: JP4273236B2; JPWO2007072691A1; JP4320434B2; JP2009096809A

Abstract

Disclosed is an organic boron π-electron system compound represented by the formula (1), wherein two boron substituents are introduced to a benzene or a substituted benzene in para-position. In the compound, a π-electron system skeleton is sterically hindered by boron substituents R1 to R4 to cause the twisting of the π-electron system skeleton. When the compound is converted into a solid state and the fluorescence quantum yield (φ) of the compound is measured, good results are obtained. Thus, the compound can emit light with high efficiency even in a solid state, and therefore is suitable as a light-emitting material (e.g., a light-emitting layer or an organic laser for an organic EL element).

Description

Specification

Organic boron π-electron compounds and synthetic intermediates thereof

Technical field

[0001] The present invention relates to a novel organoboron π-electron compound and synthetic intermediates thereof.

Background art

[0002] In recent years, the field of organic electo-tas such as organic electroluminescent devices (hereinafter referred to as organic EL) and organic lasers has attracted attention, and attempts have been made to develop excellent luminescent materials. ing. The organic light-emitting material is required to emit light with a high quantum yield, and it is widely known that the construction of a highly planar π-electron skeleton is effective for this purpose. From this point of view, π-electron compounds having a condensed polycyclic system such as anthracene and perylene, a stilbene skeleton, an oligo-phenylene skeleton, etc. in the main chain have been reported (for example, JP-A-2005-170857, JP 2005-281185 A). On the other hand, boron is introduced into the end group of the π-electron skeleton or the end group of the π-electron skeleton, and the electron structure is modified by orbital interaction between the π-electron skeleton and fluorine. Organic compounds having have been proposed. As one of such organic compounds, for example, Japanese Patent Application Laid-Open No. 2001-196183 describes that high light emission is obtained when 5,5′-bis (dimethylpolyol) 2,2′bitiophene is used as an electron transporting material. It has been reported to show brightness and high luminous efficiency.

Disclosure of the invention

[0003] However, since the π-electron compound described above generally has a highly planar π-electron skeleton, the higher the concentration, the stronger the intermolecular interaction in the solution state, the more the quenching occurs. In particular, in the solid state, this strong intermolecular interaction increases the degree of quenching. For this reason, quantum efficiency tends to decrease significantly in the solid state, and the number of luminescent materials having a high quantum yield in the solid state is extremely limited. For this reason, development of a new light-emitting material that emits light with a high quantum yield in the solid state is desired!

[0004] Further, in the electron transporting material disclosed in JP 2001-196183 A, both ends of the π-electron skeleton are used. It is also considered that intermolecular interaction is unlikely to occur because of the bulkiness and the introduction of boron substituents. However, when the present inventors investigated the quantum yield of the electron transporting material disclosed in Japanese Patent Application Laid-Open No. 2001-196183, it is said that the quantum yield in the solid state has sufficient characteristics as a light emitting material. It was difficult. In this way, there are still only a limited number of luminescent materials that have truly superior characteristics, and the development of new luminescent materials that emit light with a high quantum yield in the solid state. Was desired.

[0005] The present invention has been made in view of the above-described problems, and an object thereof is to provide a novel organoboron π-electron compound. Another object of the present invention is to provide a novel organoboron π-electron compound in which a boron substituent is introduced as a side chain to the π-conjugated skeleton. It is another object of the present invention to provide a synthetic intermediate for such an organic boron π-electron compound.

[0006] In order to suppress the quenching in the solid state, the present inventors have focused on introducing non-planarity into the π-electron skeleton by using a boron substituent as a side chain. In addition, we thought that the use of a fluorine substituent as a side chain would change the π-conjugation mode and add perturbation to the transition moment and emission wavelength. Therefore, this is a new molecular design concept, and the present invention has been completed by using a boron substituent as a side chain for the π-electron skeleton.

[0007] The organoboron π-electron compound of the present invention is a compound represented by the following formula (1) in which two boron substituents are introduced at the para position in benzene or substituted benzene. Here, the boron substituent represents BI ^ R ² and one BR ³ R ⁴ in the formula (1). The “para-position” as used herein means that the relative positions of the two substituents on the benzene ring or substituted benzene ring are at the 1- and 4-positions. In this organoboron π-electron compound, the boron substituents R ¹ , R ² , R ³ and R ⁴ used as the side chain have steric hindrance to the π-electron skeleton, and the π-electron skeleton is twisted. . As a result, the π-electron skeleton has non-planarity, and it is assumed that the degree of intermolecular interaction in the solid state can be controlled. In addition, since the boron substituent is used as a side chain, the π-electron system can be extended in a direction different from the main chain direction. Thereby, a favorable color development is shown as a luminescent material. Therefore, these organic boron π-electron compounds can be used together with luminescent materials (e.g., light emitting layers of organic EL devices and organic lasers) Suitable for _c

In the above formula (1), Ar ¹ is benzene or substituted benzene, and R ¹ , R ² , R ³ and R ⁴ are each independently a phenyl group, a substituted phenyl group, a mesityl group, a substituted mesityl group. 2,6 xylyl group, substituted 2,6 xylyl group, orthotolyl group, substituted orthotolyl group, 2,4,6 triisopropyl group, substituted 2,4,6 triisopropyl group, 2,4,6 trit-butylphenol -Group, substituted 2, 4, 6 tri-t-butylphenol group, 2, 4, 6 tris (trifluoromethyl) phenol group, substituted 2, 4, 6 tris (trifluoromethyl) phenol Group, 2,6 dialkylphenol group, substituted 2,6 dialkylphenol group, 2,4,6 trialkylphenol group, substituted 2,4,6 卜 trialkylphenol group, 2,6 diarylphenol Group, substituted 2,6 dialleyl group, 2,4,6 triarylphenol group, substituted 2,4,6 triarylphenol group, chain Nyl group, substituted chayl group, furyl group, substituted furyl group, pyrrolyl group, substituted pyrrolyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl group, anthryl group, substituted anthryl group, phenanthryl group, substituted One selected from the group consisting of a phenanthryl group, a pyrenyl group, and a substituted pyrenyl group, and π ¹ is a divalent group such as jetulbenzene, substituted jetulbenzene, dibutylbenzene, or substituted dibutylbenzene. , Benzene, substituted benzene, thiophene, substituted thiophene, pyrrole, substituted pyrrole, furan, substituted furan, pyridine, substituted pyridine, naphthalene, substituted naphthalene, anthracene, substituted anthracene, phenanthrene, substituted phenanthrene, oligoaryl group, substituted oligoaryl group , Oligo heteroaryl group, substituted oligohet Lower reel group, _α , _ω — Jetul oligoaryl group, (X, _ω — Jetul oligo hetero reel group, _α , _ω — Dibulol oligo reel group, (X, ω — Divinyl oligo hetero reel group Π ² and π ³ are each independently a monovalent group such as phenylacetylene, substituted phenylacetylene, styryl, substituted styryl, heteroarylacetylene, or substituted. Teloarylacetylene, heteroarylbull group, substituted heteroarylbull group, phenolic group, substituted phenolic Group, chael, substituted chanel, pyrrolyl, substituted pyrrolyl, furyl group, substituted furyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl, anthryl group, substituted anthryl group, phenanthryl group, substituted phenanthryl Group, oligo reel group, substituted oligo reel group, oligo hetero reel group, substituted oligo hetero reel group, oligo reel group, substituted oligo hetero group group, oligo reel group, substituted oligo hetero bin beer It is one selected from the group of fundamental forces, π ¹ and π ² are introduced in the para position into Ar ¹ , and n is a value from 0 to 400. Among them, R ¹ , R ² , R ³ and R ⁴ are 2, 4, 6-trimethyl phenol group (mesityl (Mes) group), 2, 4, 6-tris (trifluoromethyl) phenol- A bulky group such as a ruthel group, 2,4,6-triisopropylphenol group, 2,4,6-tritert-butylphenol group is preferred, and a mesityl group is particularly preferred. This is a force that sterically protects the fluorine by the mesityl group and causes steric hindrance to the π-electron skeleton and firmly fixes the steric structure. In the above formula (1), η may be 0 or 1.

Another organic boron π-electron compound of the present invention is represented by the following formula (7).

[In the formula (7), R ¹ and R ² are each independently a phenyl group, an orthoalkylphenol group, a substituted orthoalkylphenyl group, a 2,6-dialkylphenol group, , Substituted 2, 6-Dialalkylphenol, 2, 4, 6-Trialkylphenol, Substituted 2, 4, 6-Trialkylphenol, 2, 6-Diarylphenol, Substitution 2 , 6-diarylphenol, 2, 4, 6- triarylphenyl, substituted 2, 4, 6-triarylphenol, chael, substituted phenyl, furyl, substituted furyl Group, pyrrolyl group, substituted pyrrolyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl group, anthryl group, substituted anthryl group, phenanthryl group, substituted phenanthryl group, pyrenyl group, and substituted pyrenyl group strength. One kind,

R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or 1 carbon atom. To 16 branched alkyl groups, alkoxy groups, alkylthio groups, fluoroalkyl groups, aryl groups, substituted aryl groups, aryloxy groups, aryloxy groups, arylalkyl groups, aryloxy groups, arylalkylthio groups, monovalent Heterocyclic group, monovalent substituted heterocyclic group, alkyl group, substituted alkenyl group, alkyl group, substituted alkynyl group, aryl group, amino group, substituted amino group, azo group, carboxyl group, acyl group, Alkoxycarbon group, formyl group, nitro group, cyano group, silyl group, substituted silyl group, phosphino group, substituted phosphino group, silyloxy group, substituted silyloxy group, arylsulfuroxy group, alkylsulfonyloxy group, boryl A group selected from the group consisting of a group, a substituted boryl group and a neurogenic nuclear power,

R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a substituted aryl group, an aryloxy group, an aryloxy group, an arylalkyl group, an arylalkylthio group, or an arylalkylthio group. , Oligo reel group, substituted oligo reel group, monovalent heterocyclic group, monovalent substituted heterocyclic group, monovalent oligo heterocyclic group, monovalent substituted oligo heterocyclic group, alkenyl group, substituted alkenyl group, alkynyl group, Substituted alkyl group, aryl group, amino group, substituted amino group, azo group, carboxyl group, acyl group, alkoxy carbo group, formyl group, nitro group, cyan group, silyl group, substituted silyl group, stun -Group, substituted stanol group, boryl group, substituted boryl group, phosphino group, substituted phosphino group, silyloxy group, substituted silyloxy group, Reel sulfonyl O alkoxy group, alkyl Rusuruho - a Ruokishi group and one member selected from halogen nuclear group consisting,

1 is a value from 1 to 20, m is a value from 0 to 20, and n is a value from 1 to 100. Brief description of the drawings

FIG. 1 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (4a).

FIG. 2 is an explanatory diagram of an X-ray crystallographic analysis result of compound (4b).

FIG. 3 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (11).

FIG. 4 is an explanatory diagram of the results of X-ray crystallographic analysis of compound (22).

FIG. 5 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (22).

FIG. 6 is a graph showing the fluorescence spectrum of compound (23).

FIG. 7 is a graph showing the results of cyclic voltammetry measurement for compounds (22) and (26). is there.

FIG. 8 is a graph showing the fluorescence spectrum of compound (24).

FIG. 9 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (29).

FIG. 10 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (30).

FIG. 11 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (31).

FIG. 12 is a graph showing an absorption spectrum and a fluorescence spectrum of compound (32).

BEST MODE FOR CARRYING OUT THE INVENTION

The organoboron π-electron compound of the present invention is a compound represented by the above formula (1) in which two boron substituents are introduced at the para position in benzene or substituted benzene. Further, specific examples of the organic boron π-electron compound of the present invention represented by the above formula (1) are represented by the following formula (2) or (3). In this organoboron π-electron compound, an acetylene bond or an ethylene bond is introduced, and therefore the π-electron system is likely to spread in the main chain direction compared to an organoboron π-electron compound in which these bonds are not introduced. As a result, light emission tends to occur in the visible region, so it is preferred as a luminescent material.

Next, a synthesis route of the organoboron π-electron compound of the present invention represented by the above formula (1) will be described. The compound of the above formula (1) can be produced, for example, using a synthetic intermediate of the following formula (4). As an example of a route for synthesizing this synthetic intermediate of formula (4), chlorine, bromine or iodine introduced into the 2,5-positions of Ar ² using an organometallic reagent is placed on the metal. One possible route is to introduce a boron substituent into Ar ² by reacting with a halogenated boron compound such as dimesityl boron fluoride. As such an organometallic reagent, for example, organic lithium (n-BuLi, sec-BuLi, tert-BuLi, etc.), organic magnesium halide, etc. can be used. In addition, as a route for synthesizing the organoboron π-electron compound of the present invention using the synthesis intermediate of formula (4), for example, the end of the compound of formula (4) is an ethi-lou or metal ion. Route that couples the product and dinologene reel with a palladium catalyst, and a route that couples a halogenated end with jet leur or dimetalated aryl using a palladium catalyst. Can be mentioned. At this time, the organic boron π-electron compound of formula (2) can be synthesized by using the synthetic intermediate of formula (5), and the organic of formula (3) can be synthesized by using the synthetic intermediate of formula (6). Boron π-electron compounds can be synthesized. The reaction conditions such as the reaction solvent, reaction temperature, reaction time, molar concentration of substrate and reagent to be used may be appropriately set according to the reagent to be used.

In the formula (4), Ar ² is benzene or substituted benzene, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a phenyl group, a substituted phenol group, a mesityl group, Substituted mesityl group, 2,6-xylyl group, substituted 2,6-xylyl group, orthotolyl group, substituted orthotolyl group, 2, 4, 6-triisopropyl group, substituted 2,4,6-triisopropyl group, 2, 4, 6-tri-t-butylphenol, substituted 2, 4, 6-tri-t-butylphenol, 2, 4, 6-tris (trifluoromethyl) phenol, substituted 2, 4, 6— Tris (trifluoromethyl) phenol group, 2,6-dialkylphenol group, substituted 2,6-dialkylphenol group, 2,4,6-trialkylphenol group, substituted 2,4 , 6-trialkylphenol, 2, 6-diarylphenol, substituted 2, 6-diarylphenol, 2, 4, 6-triarylphenol, substituted 2, 4, 6— G Arylphenyl group, phenyl group, substituted phenyl group, furyl group, substituted furyl group, pyrrolyl group, substituted pyrrolyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl group, anthryl group, substituted anthryl group, phenanthryl group, substituted R ⁹ and R ^1C> are independently selected from the group consisting of phenanthryl group, pyrenyl group, and substituted pyrenyl group, and each of R ⁹ and R ^1C> is independently ethynyl group, trialkylsilylethyl group, alkyldiarylsilylethyl group. Group, dialkyl aryl silyl ether, triaryl silyl ether, trialkyl stan leu enyl, alkyl dia stan stan le ru, dialkyl ar lan stan le ru tur, triaryl stan le ru tulle, ar le le tur Group, substituted aryl group, oligo group Etul group, Substituted oligoaryl etulyl group, Monovalent heterocyclic ethynyl group, Substituted monovalent heterocyclic ethynyl group, Monovalent oligoheterocyclic ethynyl group, Monovalent substituted oligoheterocyclic ethynyl group, Substituted ethynyl group

, Arylebule group, substituted arylebule group, oligoreylbule group, substituted oligomeric monovinyl group, monovalent heterocyclic vinyl group, substituted monovalent heterocyclic vinyl group, monovalent oligomulticyclic bule group, monovalent Substituted oligo heterocyclic vinyl group, aryl group, substituted aryl group, oligo reel group, substituted oligo reel group, monovalent heterocyclic group, monovalent substituted heterocyclic group, monovalent oligo heterocyclic group, monovalent substituted oligo Heterocyclic group, metalated vinyl group, substituted metalated vinyl group, metalated aryl group, substituted metallized aryl group, metalated oligoreel group, substituted metallized oligoreel group, monovalent metallized heterocyclic group, monovalent Substituted metalated heterocyclic group, monovalent metalated oligoheterocyclic group, monovalent substituted metalated oligoheterocyclic group, halogenated aryl Group, halogenated aryl group, halogenated aryl group, substituted halogenated aryl group, substituted halogenated aryl group, substituted halogenated aryl group, halogenated oligomeric group, halogenated oligomeric aryl group, A halogeno-oligoaryl group, a substituted halogen-oligoaryl group, a substituted halogen-oligoaryl group, a substituted non-oligoaryl group, a monovalent halogenated heterocyclic group, a monovalent halogenated heterocyclic ethynyl group, Monovalent halogenated heterocyclic vinyl group, Monovalent substituted halogen-heterocyclic group, Monovalent substituted halogeni-heterocyclic ether group, Monovalent substituted group, Rogenated heterocyclic buyl group, Monovalent halogeno-oligo Heterocyclic group, monovalent halogenated oligo Heterocyclic ethynyl group, monovalent halogen Selected from the group consisting of a mono-substituted oligo-butyl group, a monovalent substituted halogen group, a mono-substituted halogen group, a mono-substituted halogen group, a mono-substituted halogenated oligo-heterocyclic vinyl group One kind.

In the formula (5), R ¹¹ and R ¹² are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, or a trialkylstane. -Group, alkyldiarylstanl group, dialkylarylstyl group, triarylstanol group, metallized aryl group, substituted metallized aryl group, metallized oligomeric group, substituted metallhioligo group Aryl group, monovalent metalated heterocyclic group, monovalent substituted metalated heterocyclic group, monovalent metallized oligoheterocyclic group, monovalent substituted metallized oligo heterocyclic group, aryl group, substituted aryl group , Oligo reel group, substituted oligo reel group, monovalent heterocyclic group, monovalent substituted heterocyclic group, monovalent oligo heterocyclic group, monovalent substituted oligo heterocyclic group, halogenated aryl group, substitutedヽ loginyl group, halogenated oligoreel group, substituted halogenated oligoreel group, monovalent halogenated heterocyclic group, monovalent substituted halogenated heterocyclic group, monovalent halogenated oligoheterocyclic group, and monovalent Substituted halogenated oligos of heterocyclic groups are one selected from the group consisting of

In the formula (6), R ¹³ and R ¹⁴ are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, or a trialkylstane. -Group, alkyldiarylstanl group, dialkylarylstyl group, triarylstanol group, metallized aryl group, substituted metallized aryl group, metallized oligomeric group, substituted metallhioligo group Aryl group, monovalent metalated heterocyclic group, monovalent Substituted metallized heterocyclic group, monovalent metallized oligoheterocyclic group, monovalent substituted metallized oligo heterocyclic group, aryl group, substituted aryl group, oligo reel group, substituted oligo reel group, monovalent heterocyclic group, Monovalent substituted heterocyclic group, monovalent oligoheterocyclic group, monovalent substituted oligoheterocyclic group, halogenated aryl group, substituted neurogenic group, halogenated oligoaryl group, substituted halogenated oligoreel group, monovalent A halogenated heterocyclic group, a monovalent substituted halogenated heterocyclic group, a monovalent halogeno-oligo heterocyclic group, and a monovalent substituted halogenated oligo heterocyclic group. .

Another organic boron π-electron compound of the present invention is represented by the above formula (7). In the above formula (7), R ¹ and R ² may each independently be a 2,4,6-trialkylphenol group or a substituted 2,4,6-trialkylphenol group. . Further, at least one of R ⁵ and R ⁶ may be a group represented by the following formula (8) or the following formula (9). R ³ and R ⁴ may be a hydrogen atom. Also, 1 and m may be 1, and n may be 1 or 2. 1, m and n are all 1, and R ⁵ and R ⁶ may be an aryl group, a substituted aryl group or a monovalent substituted heterocyclic group. At this time, the aryl group may be a phenyl group, the substituted aryl group may be a substituted phenyl group, and the substituted heterocyclic group may be a substituted phenyl group (eg, a diarylaminochel group such as a diphenylamino group). Yo ...

[0023] _D7

^ \

8—- (8)

R ⁸

(In Formula (8), R ⁷ and R ⁸ are each independently a phenyl group or a substituted phenyl group.)

(In the formula (9), R ⁹ and R ^1G are each independently a phenyl group or a substituted phenyl group.)

[0026] The organoboron π-electron compound of the present invention represented by the above formula (7) has a steric hindrance to the π-electron skeleton of the boron substituent—BR ² R ¹ and R ² used as the side chain. It is thought to affect. For this reason, the π-electron skeleton is twisted and has non-planarity, and the intermolecular structure in the solid state It is assumed that the degree of interaction can be controlled. As a result, the compound of the above formula (7) can have a high quantum yield in the solid state. In addition, since a boron substituent is used as a side chain, the π-electron system spreads in a direction different from the main chain direction and is considered to exhibit good light emission as a luminescent material. Therefore, the organoboron π-electron compound of the present invention is suitable as a luminescent material. Furthermore, by introducing boron, which is Lewis acid, into the side chain, the oligothiophene compound that originally tends to have hole transportability can be given electron transportability. Therefore, the organoboron π-electron compound of the present invention is suitable as a charge transport material.

Here, R ¹ and R ² in the above formula (7) include a phenyl group, an orthoalkylphenol group, a 2,6-dialkylphenol group, a 2,4,6-trialkylphenol group, Group, 2,6-diaryl furol group, 2, 4, 6-triaryl furol group, chael group, furyl group, pyrrolyl group, pyridyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and These substituents are exemplified. Specifically, the orthoalkylphenyl group includes an orthotolyl group, and an orthotamal group, and the 2,6-dialkylphenyl group includes a 2,6-xylyl group. , 6-trialkylphenol groups include mesityl group, 2, 4, 6-triisopropylphenol group, 2, 4, 6-tree tert-butylphenol group, 2, 4, 6-tris (trifluoro) ) Methylphenol group, etc. The 2,6-diarylphenol group is 2,6-bis (2-methylphenyl) phenol group, 2,6-bis (2-isopropylphenol) ) Phenol group, 2, 6-bis (2, 6-dimethylphenol) phenolic group, 2, 6-bis (2,6-diisopropylphenyl) phenol group, 2, 6-bis (2, 6-dimethylphenol) — 4 —tert-butylphenol group, etc., 2, 4, 6-triarylphenol group is 2, 4, 6-triphenyl Examples include a phenolic group and a 2,4,6-triphenylphenol group. Of these, considering the steric hindrance to the π-electron skeleton, the mesityl group is preferably 2, 4, 6-triisopropylphenol group, 2, 4, 6-tri tert-butylphenol group, 2, 4, A bulky group such as a 6-tris (trifluoro) methylphenol group, more preferably a 2,4,6-trialkylphenol group, and still more preferably a mesityl group. This is because the methoxy group provides steric protection on the boron, and also causes steric hindrance to the π-electron skeleton and firmly fixes the steric structure. In the above formula (7), R ³ and R ⁴ include a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkylthio group, a fluoroalkyl group, an alkyl group, Roxy group, aryloxy group, arylalkyl group, arylalkylalkoxy group, arylalkylthio group, aryl group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, arylaryl sulfone -Luoxy group, alkylsulfonyloxy group, and norogen atom, aryl group, monovalent heterocyclic group, alkenyl group, alkyl group, amino group, silyl group, phosphino group, silyloxy group, boryl group, and these And the like. Of these, R ³ and R ⁴ are preferably hydrogen atoms. Alternatively, one of R ³ and R ⁴ is a hydrogen atom and the other is a substituted boryl group (for example, —BR ² ), and R ⁵ and R ⁶ are substituted heterocyclic groups (for example, a substituted chenyl group such as a trialkylsilyl ether group). Is preferred.

In the above formula (7), R ⁵ and R ⁶ include a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylalkyl group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, An aryl group, a cyan group, an azo group, a carboxyl group, an acyl group, an alkoxycarbo group, a formyl group, a nitro group, an arylsulfoloxy group, an alkylsulfoloxy group and a halogen atom, an aryl group, an oligoaryl group, Monovalent heterocyclic group, monovalent oligoheterocyclic group, alkaryl group, alkyl group, amino group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, and their substituents Is mentioned. Of these groups, which group is used may be appropriately selected according to the target color of light emission. For example, when the number of thiophene rings in the π-electron skeleton is relatively small (for example, 2 to 4), when the target emission color is blue or light blue, hydrogen atoms are introduced at both ends, and the green Sometimes a group with high electron accepting properties is introduced at both ends, when it is yellow, a group with high electron accepting properties is introduced at one end, and a group with high electron donating properties is introduced at the other end, and when it is orange or red, both ends are introduced. It is also possible to introduce a group having a high electron donating property into Here, examples of the group having a high electron accepting property include a boron substituent such as a dimesitylboryl group, and examples of the group having a high electron donating property include a diphenylaminophenyl group.

[0030] Further, at least one of R ⁵ and R ^{6 in} the above formula (7) is a group represented by the above formula (8). It may be. By introducing a boron substituent having an electron accepting property as a terminal group, the electron accepting property of the organic boron π-electron compound can be improved, and the electron injection efficiency can be enhanced. Therefore, it is suitable as an electron transporting material. Also, the quantum yield of light emission in the solid state is increased. At this time, if groups represented by the above formula (8) are introduced into both ends of R ⁵ and R ⁶ , the electron accepting property and the electron injecting efficiency are improved, and a more suitable electronic structure as an electron transporting material is obtained. Can be given. In addition, R ⁷ and R ⁸ have a viewpoint power to obtain a good light emission by expanding the π-electron system, preferably a phenyl group or a substituted full group, and more preferably a mesityl group, 2, 4, 6 triisopropyl A bulky group such as a phenol group, 2, 4, 6 tri tert butyl butyl group, 2, 4, 6 tris (trifluoro) methyl phenol group, and more preferably a mesityl group. This is because the three-dimensional structure is stabilized by three-dimensionally protecting boron on the mesityl group.

[0031] Further, at least one of R ⁵ and R ^{6 in} the formula (7) may be a group represented by the formula (9). By introducing a p-aminophenyl group having an electron donating property as a terminal group, the electron donating property of the organic boron π-electron compound can be improved, and the hole injection efficiency can be increased. Also, the quantum yield of light emission in the solid state is increased. In particular, when the number of thiophene rings in the π-electron skeleton is small (for example, 2), the hole injection efficiency tends to be low in the oligothiophene part! The effect of introducing a group is high. That is, in the organoboron π-electron compound of the present invention, the hole injection efficiency is increased even when the number of thiophene rings is small, and not only the electron transport property but also the hole transport property can be provided. Therefore, it is suitable as a charge transport material. At this time, if groups represented by the above formula (9) are introduced into both ends of R ⁵ and R ⁶ , the hole injection efficiency is improved, and a more suitable electronic structure as a hole transporting material is provided. be able to. R ⁹ and R ^1C> are more preferably a phenyl group or a substituted phenyl group, and even more preferably a phenyl group, from the viewpoint of the luminous efficiency in the solid state.

[0032] 1, m and n in the above formula (7) are not particularly limited as long as they are integers. For example, R ⁵ and R may be selected as appropriate according to the target color of light emission. Regardless of ⁶ , in order for the compound of formula (7) to be bipolar (bipolar), when 1 and m are 1, n is preferably 2 or more. In this case, the compound of the above formula (7) is an electron transporting material. It is also suitable as a hole transporting material. Thus, it is assumed that the compound of formula (7) has bipolar properties because it exhibits hole transportability in the oligothiophene moiety and easily exhibits electron transportability in the borylthiophene moiety. Is done. In the organoboron π-electron compound of the present invention, 1 and m may be 1 and η may be 1 or 2.

[0033] Further, 1, m and η in the above formula (7) may be all 1, and R ⁵ and R ⁶ may be an aryl group, a substituted aryl group, or a monovalent substituted heterocyclic group (R ⁵ and R ⁶ may be the same or different). At this time, the aryl group is a phenyl group, the substituted aryl group is a substituted phenyl group (for example, 4-diphenylaminophenyl group, 4-1 rubazolyl file group, mesityl group, etc.), and the substituted heterocyclic group is substituted with a substituted chain group. Or a diarylaminochel group such as a diphenylaminochelyl group. In particular, organoboron π-electron compounds in which 1, m and η are both 1 and R ⁵ and R ⁶ are both diarylaminophenyl groups have the ability to exhibit a fluorescence maximum at around 660 nm, that is, in the red region. Compounds having such properties are not well known so far because of low band gap theory, and are highly useful in this respect.

Next, a synthesis route of the organoboron π-electron compound of the present invention represented by the above formula (7) will be described. For example, the compound of the above formula (7) can be obtained by using, for example, organic lithium (n-BuLi, sec BuLi, tert- BuLi, etc.) such as noro-oligothiophene substituted at the 3- or 4-position of the thiophene ring with a halogen atom. A route may be considered in which a boron substituent is introduced into the side chain of oligothiophene by lithiation with a boron compound and reacting with a boron halide compound. The reaction conditions such as the reaction solvent, reaction temperature, reaction time, mole concentration of the substrate and reagent to be used may be appropriately set according to the reagent to be used.

[0035] In the compounds of the above formulas (7) to (9), among the substances listed as ^ to! ^ ^{1 ()} , an alkyl group, an orthoalkylphenol group, a 2,6 dialkylphenol group, 2 , 4, 6 Trialkyl alkyl groups, alkylthio groups, arylalkyl groups, arylalkylthio groups, alkylsulfo-oxy groups, and the like include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n Butyl group, isobutyl group, sec butyl group, tert-butyl group, etc., alkoxy group, aryloxy group, alkoxycarbo- Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group. Examples of the alkenyl group include a vinyl group, an aryl group, a butyr group, and a styryl group. Examples of the alkynyl group include an ethuryl group, a propargyl group, a phenylacetyl group, an aryl group, an aryloxy group, an aryl group, an aryl alkyl group, an aryl alkyl alkoxy group, an aryl alkylthio group, an aryl sulfo group. 2, 6-diarylphenol, 2,4,6-triarylphenol, etc. include phenyl, 2,6-xylyl, mesityl, duryl, biphenyl, and the like. Group, terfel group, naphthyl group, anthryl group, pyrenyl group, tolyl group, acyl group, fluorophenol group, diphenyl group Examples include a phenol group, a dimethylaminophenol group, a jetylaminophenol group, a phenanthrenyl group, and the oligoaryl group includes an oligoparaphenylene, an oligofluorene, and an Rigo (paraphenolic lenylene). , Oligo (para-phenylene-ethylene), etc., and monovalent heterocyclic groups include furyl, chenyl, pyrrolyl, pyridyl, benzochel, quinolyl, etc. Examples of the oligoheterocyclic group include oligofuran, oligothiophene, oligopyridine, oligobenzobenzothiophene, and the halogen atom includes a fluorine atom, a chlorine atom, and the like.

, Bromine atom, iodine atom and the like.

In the organic boron π-electron compound of the present invention, among the listed substances, specific substituents of those prefixed with “substitution” include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. A halogen atom, a methyl group, an ethyl group, a η-propyl group, an isopropyl group, a η-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an alkyl group; a cyclopentyl group Cyclic alkyl groups such as a cyclohexyl group; Alkenyl groups such as a vinyl group, an aryl group, a butenyl group, and a styryl group; an alkynyl group such as an ethynyl group, a propargyl group, and a fluoracetinyl group; a methoxy group, an ethoxy group, Alkoxy groups such as isopropoxy group and tert-butoxy group; alkoxy groups such as buroxy group and arryloxy group; eturoxy group And alkenyloxy groups such as phenacetyloxy groups; aryloxy groups such as phenoxy groups, naphthoxy groups, biphenyloxy groups, pyrenyloxy groups; perfluoro groups such as trifluoromethyl groups, trifluoromethoxy groups, and pentafluoroethoxy groups Group and even longer chain perfluoro Amino group such as dimethylamino group, jetylamino group, diphenyl-lumino group, carbazolyl group; boryl group such as diphenylpolyl group, dimesitylboryl group, bis (perfluorophenyl) boryl group; acetyl group or benzoyl group Carbonyl groups such as acetooxy groups and benzoyloxy groups; alkoxy carbonyl groups such as methoxy carbo yl groups, ethoxy carbonyl groups and phenoxy carbo ol groups; methyl sulf yl groups and sulphyl sulfyl groups Sulphiel groups such as trimethylsilyl groups, triisopropyl silyl groups, dimethyl-tert-butylsilyl groups, trimethoxysilyl groups, tributylsilyl groups, etc .; phenyl groups, 2,6-xylyl groups, mesityl groups, duryls Group, biphenyl group, terfel group, naphthyl group, ant Aryl groups such as a tolyl group, a pyrenyl group, a tolyl group, an amino group, a fluorophenyl group, a diphenylaminophenol group, a dimethylaminophenol group, a jetylaminophenol group, a phenanthrenyl group; Chayl group, furyl group, silacyclopentagenyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, attaridinyl group, quinolyl group, quinoxaloyl group, phenanthryl group, benzochelyl group, benzothiazolyl group, Examples thereof include heterocyclic groups such as indolyl group, carbazolyl group, pyridyl group, pyrrolyl group, benzoxazolyl group, pyrimidyl group and imidazolyl group. In addition, a nitro group, a formyl group, a nitroso group, a formyloxy group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a cyano group and the like can be mentioned. Further, these substituents may be bonded to each other at any position to form a ring.

The organoboron π-electron compound of the present invention can be used as a light-emitting material such as an organic EL device or an organic laser. Here, as an example, a case where the organic EL device is used as a light-emitting material will be described. An organic EL element has a structure in which three thin films, a hole transport layer, a light-emitting layer, and an electron transport layer, are sandwiched between two electrodes. Holes injected from the anode are transferred to the light-emitting layer through the hole-transport layer. Then, electrons injected from the cathode enter the light emitting layer (layer mainly composed of a light emitting material) through the electron transport layer, so that holes and electrons recombine in the light emitting layer to emit light. Each layer that constitutes the organic EL element is formed by forming the material that constitutes each layer into a thin film by a known vapor deposition method or spin coating method. When thinning using a vapor deposition method, the vapor deposition conditions depend on the type of material that should form each layer and the purpose of the molecular accumulation film. Different forces depending on the crystal structure and the associating structure, etc. For example, boat heating temperature 50 ~ 40 0 ° C, vacuum degree 10-6 ~: LO-3Pa, deposition rate 0.01 ~ 50nmZs, substrate temperature -50 ~ + 300 ° C, film thickness 5 ~ 5000nm can be selected as appropriate! / ヽ.

Next, a method for producing an organic EL element using the organoboron π-electron compound of the present invention will be described. A thin film with anode material strength on an appropriate substrate is formed by vapor deposition to a thickness of 1 μm or less, preferably in the range of 10 to 2 OOnm. A thin film made of a material is formed by vapor deposition to form a hole transport layer. Subsequently, a thin film made of the organoboron π-electron compound of the present invention is formed on the formed hole transport layer by an evaporation method to form a light emitting layer, and a thin film made of an electron transport material is further formed thereon by an evaporation method. It is formed as an electron transport layer. Then, an organic EL device can be obtained by forming a cathode on the formed electron transport layer by a vapor deposition method so as to have a thickness of 1 μm or less as a negative material force. In the production of the organic EL element described above, the production order may be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, and the anode may be produced in this order.

[0039] The anode of the organic EL element is composed of, for example, an electrode material having a high work function. Specifically, a metal such as gold, an alloy such as copper iodide, indium tinoxide, Dielectric transparent material power such as zinc oxide is also configured. For example, the cathode of the organic EL element may be composed of an electrode material having a low work function. Specifically, calcium, magnesium, lithium, aluminum, magnesium alloy, aluminum Z lithium mixture, magnesium / A silver mixture, indium force may also be configured. The hole transport layer of the organic EL element is composed of, for example, a polymer having a main chain or a side chain of an aromatic tertiary amine such as N-carbcarbazole, polycarbcarbazole, or the like, TPD, or aromatic tertiary amine. —Triarylamine derivatives such as bis (4 di-p-triaminophenol) cyclohexane and N, N, 1-diphenyl-N, N, -dinaphthyl-4,4, -diaminobiphenyl, copper phthalocyanine, etc. Phthalocyanine derivatives, polysilanes, and the like. The electron transport layer of the organic EL device includes, for example, tris (8-hydroxyquinolinate) aluminum (Alq), a polymer of certhiazole, 1, 3, 4 oxazole derivatives, 1, 2, 4

Three

-It may be a triazole derivative. Example 1

[0040] (1) Synthesis of 2,5 bis (dimesitylboryl) 1,4 bis (trimethylethyl) benzene First, 2,5 dib-mouthed 1,4 bis (trimethylsilylethyl) benzene (compound 1) 1,4 Jib port Mo 2,5 Jodobenzene was synthesized by a known method (J. 0 rganomet. Chem. 2002, 653, 215.) as a starting material. Subsequently, n-BuLi (l. 6M, 13. lm L, 21. Ommol) was added to the THF solution (80 mL) of Compound 1 (4. 36 g, 10. Ommol) at -78 ° under an argon gas atmosphere. Added dropwise with C. Stirring was continued for 30 minutes while maintaining the reaction solution at −78 ° C., and then a THF solution (30 mL) of dimesityl boron fluoride (8.07 g, 21. Ommol) was added thereto. The reaction solution was slowly warmed to room temperature and stirred at room temperature overnight. The solvent was distilled off under reduced pressure, and the residue was washed with ether and recrystallized from a mixed solvent of hexane and chloroform. 4.47 g (5.80 mmol) of 2,5 bis (dimesitylboryl) — 1 , 4 Bis (trimethylethynyl) benzene (compound 2 below) was obtained as a white solid in a yield of 58%. The spectral data of Compound 2 is as follows: mp> 300 ° C; 1H NMR (CDC1): d -0.06 (s, 1

Three

8H), 1.99 (s, 24H), 2.27 (s, 12H), 6.75 (s, 8H), 7.34 (s, 2H); ¹³ C NMR (CDC1): d0.3

Three

, 21.3, 23.3, 99.1, 104.8, 125.7, 128.4, 137.4, 139.3, 140.9, 142.4, 152.6; HRMS (FAB): 766.4750 (M "); Cald for C H B Si: 766.4733.

52 64 2 2

[0041]

Compound 1 Compound 2

[0042] (2) Synthesis of 2, 5-bis (dimesitylboryl) 1,4 jetulbenzene

Under an argon gas atmosphere, a THF solution (lOOmL) of compound 2 (1.53 g, 2. Ommol) was charged with a THF solution of T BAF (1. OM, 40 mL, 40 mmol) at room temperature. Stir for days. After distilling off the solvent under reduced pressure, the resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z chloroform = 5 Zl, Rf = 0.35). Further, recrystallization was performed with a mixed solvent of hexane and chloroform, and 0.85 g (l. 34 mmol) of 2,5 bis (dimesitylboryl) 1,4-jetulbenzene (compound 3 below) was added to white. Obtained as a colored solid in 68% yield. The spectral data of Compound 3 are as follows: mp> 30 0 ° C; ^J H NMR (270 MHz, CDCl): d2.00 (s, 24H), 2.27 (s, 12H), 2.74 (s, 2H), 6.75 (

Three

s, 8H), 7.39 (s, 2H); ¹³ C NMR (100 MHz, CDCl): d 21.3, 23.2, 81.5, 83.1, 125.1, 1

Three

28.2, 137.8, 139.4, 140.9, 142.3, 153.0; HRMS (FAB): 623.4020 (M + H +); Calcd for C H B: 623.4036.

Compound 2 Compound 3

[0044] (3) Synthesis of 2,5-bis (dimesitylboryl) 1,4-bis (feature) benzene Under an argon gas atmosphere, compound 3 (62 mg, 0.10 mmol), oodobenzene (82 mg, 45 ^ L, 0.40 mmol), Pd (PPh) (12 mg, 0. Olmmol) and Cul (3.8 mg, 0.0.0)

3 4

2 mmol) was degassed into a mixed solution of 1/3 (v / v) (i—Pr) NEt / THF (4 mL) at room temperature.

2

Melted. The reaction solution was stirred at 50 ° C. overnight. After the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform. This solution was mixed with 5% NH 4 OH aqueous solution, IN HC1 aqueous solution and saturated saline.

Four

After washing with anhydrous MgSO 4, the filtrate was concentrated under reduced pressure after suction filtration. Gain

Four

The resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z-cloform = 5 Zl, Rf = 0.30) and 56 mg (0.072 mmol) of 2,5 bis (dimesitylboryl) 1, 4 Bis (feature-benzene) benzene (compound 4a below) was obtained as a green solid in a yield of 72%. The spectral data of compound 4a is as follows. Mp 296.5-297.5. C; 'Η NMR (CDCl): d 2.04 (s, 24H), 2.26 (s, 12H), 6.76 (s, 8H), 6.98 (dd, J = 7.2, 1.

Three

6 Hz, 4H), 7.15-7.20 (m, 6H), 7.46 (s, 2 H); ¹³ C NMR (CDCl): d21.2, 23.3, 90.2, 9

Three

3.8, 123.2, 125.9, 127.7, 127.9, 128.4, 131.5, 137.5, 139.2, 140.9, 142.5, 152.2; EI MS m / z 774 (M ⁺ ); Anal.Calcd for CHB: C 89.92, H 7.29. Found: C 90.14, H 7.

58 52 2

43.

Compound 4a R = H

Compound 4b R = N Ph ₂

Compound 4c R = Cz

[0046] (4) X-ray crystal structure analysis

X-ray crystal structure analysis was performed on the compound 4a synthesized in this way. Figure 1 shows the results. As shown in Figure 1, among the benzene rings in the π-electron skeleton of compound 4a, the benzene ring introduced with a boron substituent and the benzene ring bonded to this benzene ring via an acetylene bond are dihedral angles. 37. 28 ° was formed, and it was confirmed that the π-electron skeleton was twisted. This is presumed that steric hindrance was caused by the boron substituent into which two mesityl groups were introduced, and this steric hindrance caused a twist between the two benzene rings. The steric structure of Compound 4a was firmly fixed by the boron substituent.

[0047] (5) Preparation of spin coat film and powder

In examining the fluorescence quantum yield in the solid state of Compound 4a, a spin coat film and a powder of the obtained Compound 4a were prepared. Of these, a spin coat film was prepared on a quartz substrate using a THF solution prepared by setting the concentration of compound 4a to about 1 mgZO. 25 mL. The powder was obtained by distilling off the solvent under reduced pressure after purification.

[0048] (6) Measurement of spectrum and measurement of fluorescence quantum yield

The obtained spin coat film and powder are measured for absorption spectrum and fluorescence spectrum using a fluorescence spectrometer F4500 (manufactured by Hitachi), and using a quantum yield measuring device C9920-01 (manufactured by Hamamatsu Photonitas). The fluorescence quantum yield was measured. Table 1 shows the measurement results. First, as shown in Table 1, the absorption spectrum of the spin coat film showed an absorption maximum at 360 nm. When photoexcited at this wavelength, it showed a fluorescence maximum at 484 nm. Also, The powder showed an absorption maximum at 360 nm and a fluorescence maximum at 498 nm. Next, when the fluorescence quantum yield (Φ) was measured, as shown in Table 1, φ = 0.44 for the spin coat film and φ = 0.71 for the powder. These values are sufficient quantum yields for the light-emitting material, and it was confirmed that Compound 4a exhibits high-efficiency light emission in the visible region in the solid state, particularly in the powder. In addition, in order to confirm the effect of introducing boron substituents, a spin coat film was prepared in the same manner for 1,4-bis [(4-diphenylamino) phenol] etchurebenzene (compound 5 below) as a comparative example. When the fluorescence quantum yield φ was measured, it was 0.19. From this, it can be said that the high-efficiency fluorescent quantum yield was obtained with the compound 4a due to the influence of the boron substituent. In other words, it is presumed that the π-electron skeleton of compound 4a is twisted and this three-dimensional structure is firmly fixed, so that the intermolecular interaction in the solid state is weakened, thereby suppressing quenching. .

[0049] [Table 1]

* Not implemented

Compound 5 Example 2

[0051] (1) 2, 5 Bis (dimesitylboryl) 1, 4 Bis [(4-Diphenylamino) phenol] Synthesis of tulubenzene

Under an argon gas atmosphere, compound 3 (62 mg, 0, 10 mmol), 4-diphenylamino 1 odobenzene (l l lmg, 0.30 mmol), Pd (PPh) (12 mg, 0. Olmmol) and

3 4

Cul (3.8 mg, 0.02 mmol) degassed lZ3 (vZv) (i—Pr) NEtZTHF (4 mL)

2

The mixed solution was dissolved at room temperature. The reaction solution was stirred at 50 ° C. overnight. The solvent was distilled off under reduced pressure, and then dissolved in black mouth form. 5% NH 4 OH aqueous solution, IN HC1 aqueous solution

Four

Solution and saturated brine, dried over anhydrous MgSO, and filtered with suction to remove the desiccant.

Four

After removal, the mixture was concentrated under reduced pressure. The resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z-chloroform = 3Zl, Rf = 0.22), and 56 mg (0.05 5 mmol) of 2,5 bis (dimesitylboryl) 1, 4 Bis [(4 diphenylamino) phenyl] ethynylbenzene (Compound 4b) was obtained as a green solid in a yield of 59%. The spectral data of Compound 4b are as follows: mp 296.5-297.5 ° C; ^J H NMR (CDC1): d 2.04 (s,

Three

24H), 2.26 (s, 12H), 6.76 (s, 8H), 6.98 (dd, J = 7.2, 1.6 Hz, 4H), 7.15-7.20 (m, 6H), 7.46 (s, 2H); ¹³ C NMR (CDC1): d21.2, 23.3, 90.2, 93.8, 123.2, 125.9, 127.7, 127.

Three

9,128.4, 131.5, 137.5, 139.2, 140.9, 142.5, 152.2; EI MS m / z 774 (M ⁺ ); Anal.Calcd for CHB: C 89.92, H 7.29. Found: C 90.14, H 7.43.

58 52 2

[0052] (2) X-ray crystal structure analysis

The compound 4b synthesized in this way was subjected to X-ray crystal structure analysis. Figure 2 shows the results. As shown in Fig. 2, of the benzene rings in the π-electron skeleton of compound 4b, the benzene ring introduced with a boron substituent and the benzene ring bonded to this benzene ring via an acetylene bond are dihedral angles. 47. 53 ° was formed, and it was confirmed that the π-electron skeleton was twisted.

[0053] (3) Measurement of spectrum and measurement of fluorescence quantum yield

The spin coat film and powder of compound 4b were prepared in the same manner as in Example 1 (5) above, and the absorption spectrum and fluorescence spectrum were measured and the fluorescence quantum yield was measured in the same manner as in Example 6 (6) above. The rate was measured. As a result, the spin coat film showed an absorption maximum at 360 nm and a fluorescence maximum at 560 nm. The powder showed an absorption maximum at 360 nm and a fluorescence maximum at 570 nm (see Table 1). Fluorescence quantum yield φ is φ for spin coat film = 0.94, and in the powder, φ = 0.87. These values were extremely good as quantum yields, and it was confirmed that Compound 4b exhibits highly efficient light emission in the visible region in the spin coat film and powder.

Example 3

[0054] (1) Synthesis of Compound 4c

Under an argon gas atmosphere, compound 3 (62 mg, 0.1 mmol), 9 (p-) odor-foil;) force rubazole (147 mg, 0.30 mmol), Pd (PPh) (12 mg, 0. Olmmol) and Cu

3 4

1 (3.8 mg, 0.02 mmol) degassed with lZ3 (vZv) (i— Pr) NEtZTHF (4 mL)

2

This was dissolved in the combined solution at room temperature and stirred at 50 ° C. overnight. After the solvent was distilled off under reduced pressure, the residue was dissolved in black mouth form. This solution was mixed with 5% NH OH aqueous solution, IN HC1 aqueous solution and saturated solution.

Four

After washing with brine, drying over anhydrous MgSO and removing the desiccant by suction filtration

Four

The filtrate was concentrated under reduced pressure. The obtained mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z chloroform form = 4Zl, Rf = 0.11) to obtain 101 mg (0.092 mmol) of the above compound 12c of the above formula 12 as a green solid. As a yield of 92%. The spectrum data of compound 4c are as follows: mp> 300 ° C; ^J H NMR (CDCl): d 2.10 (s, 24H), 2.28 (

Three

s, 12H), 6.82 (s, 8H), 7.22 (d, J = 8.4 Hz, 4H), 7.28 (t, J = 7.2 Hz, 4H), 7.36-7.44 (m, 12H), 7.55 (s, 2H ), 8.13 (d, J = 8.4 Hz, 4H); ¹³ C NMR (CDCl): d 21.3, 23.4, 91.

Three

2, 93.2, 109.7, 120.1, 120.3, 122.2, 123.5, 125.9, 126.0, 126.3, 128.5, 133.1, 137.2, 137.8, 139.4, 140.6, 141.0, 142.5, 152.3; EI MS m / z 1104 (M "); Anal Calcd for CHBN: C, 89.12, H 6.38, N 2.53. Found: C, 88.89, H 6.59, N 2.56.

82 70 2 2

[0055] (2) Measurement of spectrum and measurement of fluorescence quantum yield

The spin coat film and powder of compound 4c were prepared in the same manner as in Example 1 (5) above, and the absorption spectrum and fluorescence spectrum were measured and the fluorescence quantum yield was measured in the same manner as in Example 1 (6) above. The rate was measured. As a result, the spin coat film showed an absorption maximum at 360 nm and a fluorescence maximum at 505 nm. The powder showed an absorption maximum at 360 nm and a fluorescence maximum at 504 nm (see Table 1). The fluorescence quantum yield φ was φ = 0.84 for the spin coat film and φ = 0.99 for the powder. These values are extremely good quantum yields, and compound 4c is highly effective in the visible region in the spin coat film and powder. It was confirmed that the light emission was high.

Example 4

[0056] (1) Synthesis of 2, 5 bis (dimesitylboryl) -4 eth-lu 1-trimethylsilylethyl benzene

Under an argon gas atmosphere, THF solution (1 OM, 4. OmL, 4. Ommol) of T BAF was added to THF solution (lOOmL) of compound 2 (1.53 g, 2. Ommol) at room temperature, and the reaction solution Was stirred at room temperature for 2 days. After distilling off the solvent under reduced pressure, the resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z-chloroform = 5Zl, Rf = 0.38). Further, the product was purified by GPC (solvent: chloroform), and 1.01 g (l. 45 mmol) of 2,5 bis (dimesitylboryl) -4-ethyl-1 trimethylsilylethylbenzene (compound 6 below) was collected as a white solid. Obtained at a rate of 73%. The spectral data of Compound 6 are as follows: m p 237.5-238.5-'NMR (CDCl): d -0.06 (s, 9H), 1.98 (s, 12H), 2.00 (s, 12H), 2.

Three

26 (s, 6H), 2.28 (s, 6H), 2.73 (s, lH), 6.74 (s, 4H), 6.75 (s, 4H), 7.33 (s, 1H), 7.39 (s, 1H); ¹³ C NMR (CDCl): d- 0.4, 21.2, 21.3, 23.2, 23.3, 81.4, 83.2, 99.2, 104.6, 12

Three

4.6, 126.1, 128.1, 128.4, 137.4, 137.8, 139.3, 139.4, 140.8, 141.0, 142.4, 152.6, 15 3.0; HRMS (FAB): 695.4432 (M + H ⁺ ); Calcd for CHB Si: 695.4416.

49 57 2

[0 ()

Compound 2 Compound 6

[0058] (2) 2, 5 Bis (dimesitylboryl) -4 Synthesis of benzene-rutrimethylsilylethyl benzene

Compound 6 (138 mg, 0.20 mmol), odobenzene (163 mg, 90 ^ L, O. 80 mmol), Pd (PPh) (23 mg, O. 02 mmol) and Cul (7.6 mg, O under argon gas atmosphere .

3 4

04 mmol) was degassed in a mixed solution of 1Z3 (v / v) (i—Pr) NEt / THF (8 mL) at room temperature.

2

It melted with. The reaction solution was stirred at 50 ° C. overnight. After the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform. This solution was mixed with 5% NH 4 OH aqueous solution, IN HC1 aqueous solution and saturated saline.

Four

After washing with anhydrous MgSO and drying with anhydrous MgSO and removing the desiccant by suction filtration, the filtrate Was concentrated under reduced pressure. The resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z chloroform = 5Zl, Rf = 0.34), and 138 mg (0.18 mmol) of 2,5 bis (dimesitylboryl) -4 phenol Lucy-rutrimethylsilylethylbenzene (the following compound 7) was obtained as a pale yellow solid in a yield of 90%. The spectral data of Compound 7 are as follows: mp 285.0-286.0 ° C; 1H NMR (CDCl): d -0.05 (s, 9H), 2.02 (s,

Three

24H), 2.26 (s, 6H), 2.28 (s, 6H), 6.76 (s, 8H), 6.97 (dd, J = 6.8, 1.6 Hz, 2 H), 7.13 -7.19 (m, 3 H), 7.39 (s, 1 H), 7.40 (s, 1H); ¹³ C NMR (CDCl): d = —0.3, 21.2, 21.3,

Three

23.3, 90.1, 93.8, 98.9, 104.9, 123.1, 125.6, 125.9, 127.7, 127.8, 128.37, 28.39, 131.5, 137.1, 137.7, 139.2, 139.3, 140.9, 141.0, 142.5, 152.0, 152.8; HRMS (FAB) : 770 .4669 (M ⁺ ); Cald for CHB Si: 770.4650.

55 60 2

Compound 6 Compound 7

(3) Synthesis of 2,5 bis (dimesitylboryl) -4 eth-roof erethylbenzene Under argon gas atmosphere, THF solution (5 mL) of compound 7 (191 mg, 0.25 mmol) in THF solution of T BAF (1.0 M , 2.5 mL, 2.5 mmol) was added at room temperature, and the reaction solution was stirred at room temperature for 4 days. After distilling off the solvent under reduced pressure, the resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z-chloroform = 5 Zl, Rf = 0.32), and 1 51 mg (0.22 mmol) of 2,5 Bis (dimesitylboryl) -4-etulyl-feruylbenzene (compound 8 below) was obtained as a pale yellow solid in a yield of 87%. The spectrum data of Compound 8 are as follows: mp 154.0-155.0 ° C; 1H NMR (CDCl): d 2.03 (s, 12H),

Three

2.05 (s, 12H), 2.26 (s, 6H), 2.30 (s, 6H), 2.76 (s, 1H), 6.76 (s, 4H), 6.78 (s, 4H), 6.98 (dd, J = 6.8, 1.6 Hz, 2 H), 7.15-7.21 (m, 3H), 7.42 (s, 1H), 7.47 (s, 1H); ¹³ C NM R (CDCl): d21.2, 21.3, 23.2, 23.3, 81.3, 83.3, 89.9, 93.9, 123.0, 124.5, 126.4, 127

Three

.7, 127.9, 128.2, 128.4, 131.5, 137.1, 138.2, 139.2, 139.4, 140.8, 141.0, 142.4, 151 .9, 153.2; HRMS (FAB): 698.4272 (M "); Cald for CHB: 698.4255.

Compound 7 Compound 8

[0062] (4) Synthesis of 1, 4 bis {[2, 5 bis (dimesitylboryl)-4 phe-lature- 1- pheyl] ethynyl} benzene

Under an argon gas atmosphere, compound 8 (110 mg, 0.16 mmol), p-jodobenzene (2 6 mg, 0.08 mmol), Pd (PPh) (18 mg, 0.016 mmol) and Cul (l. 6 mg, 0.03)

3 4

2

Dissolved and stirred at 50 ° C. overnight. After distilling off the solvent under reduced pressure, it was dissolved in black mouth form. This solution was washed with 5% NH 4 OH aqueous solution, IN HC1 aqueous solution and saturated saline.

Four

After drying with anhydrous MgSO and removing the desiccant by suction filtration, the filtrate was reduced under reduced pressure.

Four

Concentrated with. The resulting mixture was separated and purified by silica gel chromatography (developing solvent: hexane Z chloroform = 5Zl, Rf = 0.25), and 110 mg (0.075 mmol) of 1,4-bis {[2,5 bis (Dimesitylboryl) -4 methanol 1 methanol] benzene} Benzene (compound 9 below) was obtained as a green solid in a yield of 93%. The spectral data of Compound 9 are as follows: mp 294-295 ° C; H NMR (CDC1): d 2.02 (s, 24H), 2.03 (s, 2

Three

4H), 2.27 (s, 24H), 6.74 (s, 16H), 6.77 (s, 4H), 6.94 (dd, J = 7.8, 1.6 Hz, 4 H), 7.13 -7.19 (m, 6H), 7.39 ( s, 2H), 7.41 (s, 2H); ¹³ C NMR (CDC1): d 21.21, 21.24, 23.1, 9

Three

0.1, 91.8, 93.9, 94.2, 122.3, 123.0, 125.4, 125.8, 127.4, 127.5. 128.3, 130.6, 131.3, 137.45, 137.49, 138.8, 140.3, 142.0, 151.5, 151.6; EI MS m / z 1471 (M ⁺ ) Anal. Calcd for CHB: C, 89.80; H, 7.26. Found: C, 89.79; H, 7.36.

Mes _z B Mes ₂ B

Compound 9

[0064] (5) Measurement of spectrum and measurement of fluorescence quantum yield

A spin coat film of Compound 9 was prepared in the same manner as in Example 1 (5) above, and the absorption spectrum and fluorescence spectrum and fluorescence quantum yield were measured in the same manner as in Example 1 (6) above. And went. As a result, it showed an absorption maximum at 389 nm and a fluorescence maximum at 488 nm (see Table 1). The fluorescence quantum yield φ was φ = 0.59. From this, it was confirmed that the compound 9 emits light with relatively high efficiency in the visible region in the spin coat film.

Example 5

[0065] (1) Synthesis of 2, 5 bis (dimesitylboryl) 1,4 bis {2— [4 (diphenylamino) phenol] vinyl} benzene

First, 2, 5 Jib Mouth 1, 4 Bis {2— [4— (Diphenylamino) phenol] bur} Benzene (compound 10 below) is converted to [2, 5 Jib Mouth Mor 4 (Diethoxyphosphorylmethyl) [Benzyl] phosphonic acid jetyl ester and 4 (diphenylamino) benzaldehyde were synthesized by known methods (J. Am. Chem. Soc. 2001, 123, 1215.) as starting materials. Subsequently, t-BuLi (1.46M in heptane, 0.86 mL, 1.26 mmol) was added to a THF solution (5 mL) of compound 10 (231 mg, 0.30 mmol) in an argon gas atmosphere. C was slowly dropped. The reaction solution was stirred at −78 ° C. for 1 hour, and a solution of dimesityl boron fluoride (168 mg, 0.6 3 mmol) in THF (5 mL) was added. The reaction solution was slowly warmed to room temperature and stirred overnight at room temperature. After adding water (5 mL), the aqueous layer was extracted with black mouth form (30 mL). The organic layer was dried over anhydrous MgSO, filtered under suction and concentrated under reduced pressure. The resulting blend

Four

The compound was chromatographed on silica gel (developing solvent: hexane Z-chloroform = 5Zl, Rf ¾¾¾

Ό = Φ

4—c, «e, ^ Φ ¾ί 士晷. (^ Fist "[挲 Ρ · Π ¥ ¾ ¾ ^ ^rau 96S

, One

. Thigh> ¾τ 士晷

¾ thigh ¾1 晷晷, ¥ thigh ΟΗβ ^^ (ε) [8900]

081 9¾¾ni ^?濰 be be: ^^

^^^ 濰 bebe ^ e ^^ be ^ e; 濰 bebe> ^ ί ^ Υ ^ Kouki 濰濰 pebe> ^) ψ 晷蜜士篡 u 呦 ^ ^ ^ ζΤ-^ ε® . ·

^ wM ^ m z) 900]

χη) ζιπ ζ / η sn m -O ST '^ Hi' £ η 's'ow'z'o's'6si' ε ε ΐ '9 · οει'ζ'βζι'vszi' νιζι 'τιζι

Ίτζι 'υζζι' ζτζ 'ζ'ΐζ ρ-(Ό

QD) ^ ηη _εΐ '(Η2' s) 09 "Z '{' ^Ζ Η 9ΐ = ['Ρ) WL' (Η9ΐ 'ω) SO'L-WL' (Η8ΐ 'ω) 06 · 9- ΐ8 · 9 '{ΗΖ' ^Ζ Η 0 · 9ΐ = f 'Ρ) Ζ' 9 '{ΗΖ \ ^<s ) 9Ζ'Ζ' (Η W ^<s ) Ρ-(OQD) Awakening

6 _Τ '6) ¾ ：； 0) Stop «« One ^ 4 ^ ： 0) 11 呦 ^]

¾ (υ 呦 ^ ¾stop) bebe: ^ {-[-e (, ^ -e Ο → ~] -Z} ^ → '

I-

, Tsu 灞 (St Ό =

L9 Z £ / 900ZdT / 13d 83 Ϊ69Ζ.0 / .00Ζ OAV The quantum yield was sufficient as a material, and it was confirmed that Compound 11 exhibits highly efficient light emission in the visible region in the spin coat film and powder. In addition, in order to confirm the effect of introducing the boron substituent, a spin coat film of 1, 4 bis {2- [4 (diphenylamino) phenyl] bulle} benzene (compound 12 below) was similarly prepared as a comparative example. Then, when the fluorescence quantum yield Φ was measured, it was φ = 0.06. From this, it can be said that the high-efficiency fluorescence quantum yield obtained with Compound 11 is due to the influence of the boron substituent. In other words, it is presumed that the π-electron skeleton of compound 11 is twisted and the three-dimensional structure is firmly fixed, so that the intermolecular interaction in the solid state is weakened, thereby suppressing quenching.

Compound 1 2

Example 6

[0070] (1) Synthesis of 3 Dimesitylbolyl 2, 2, 1-bithiophene

3 Bromo-2,2,1-bithiophene (compound 21 below) 3. 49 g (13.7 mmol) was dissolved in ether (20 mL), and n-BuLi (l. 6M, 9. OmL, 14.4 mmol) was dissolved at -78 °. C was added dropwise and stirring was continued for 3 hours. To this solution, add Mes BF (4.05 g, 15. lmm at 78 ° C.

2

ol) in ether (20 mL) was added dropwise. The reaction solution was slowly returned to room temperature and stirred at room temperature overnight. Water (20 mL) was added, and the aqueous layer was extracted 5 times with hexane (10 mL). Combine the organic layers, dry over MgSO, filter under reduced pressure and concentrate with evaporation.

Four

A brown solid was obtained. Recrystallized from a mixed solution of hexane: toluene (1: 1), 3 dimesityl boriloux 2, 2 'bitophene (compound 22 below) 1.16g (2.81mmol) as a yellow-green solid in 20% yield Obtained. Further, the filtrate was purified by silica gel column chromatography (hexane: toluene = 7: 1, Rf = 0.40), and 3 dimesitylboryl 2,2,1, bithiophene (Compound 22). 2. 43 g (5. 87 mmol) were obtained with a yield of 43%. In other words, Compound 22 was obtained in a yield of 63% as 3.59 g (8.68 mmol) of a yellowish green solid. Trace melting point measurement When the melting point of the obtained solid was measured with a constant apparatus (manufactured by Yanakone, MP-S3), the melting point was 129.3-129.8 ° C. The spectrum data is as follows.

[0071] 1H NMR (400 MHz, CDC1) δ 2.02 (s, 12H), 2.21 (s, 6H), 6.65 (s, 4H), 6.67 (dd, J

3 H

= 5.2, 3.6 Hz, 1H), 6.75 (dd, J = 3.6, 1.2 Hz, 1H), 6.89 (d, J = 4.8 Ηζ, ΙΗ), 7.0

H HH HH

3 (dd, J = 5.2, 1.2 Hz, 1H), 7.19 (d, J = 4.8 Hz, 1H); ¹³ C NMR (100 MHz, CDC1)

HH HH 3 δ 21.2, 23.0, 124.6, 126.2, 126.7, 127.0, 128.1, 135.1, 136.5, 138.6, 140.6, 142.2, 146.0, 147.7; ⁿ B NMR (128 MHz, CDC1) δ 69.2.Unit: ppm. Anal. Calcd for CH

3 26 2

BS: C, 75.35; H, 6.57; N, 0.00. Found: C, 75.10; H, 6.53; N, 0.00.

7 2

[0072]

Compound 21 Compound 22

[0073] (2) X-ray crystal structure analysis

Compound 22 thus synthesized was subjected to X-ray crystal structure analysis. Figure 4 shows the results. As shown in FIG. 4, the thiophene rings in the π-electron skeleton of Compound 22 form a dihedral angle of 56.3 °, confirming that the π-electron skeleton is twisted. This is presumed that steric hindrance was caused by the boron substituent into which the mesityl group was introduced, and this steric hindrance caused a twist between the two thiophene rings. The three-dimensional structure of Compound 22 was firmly fixed by a boron substituent.

[0074] (3) Preparation of spin coat film

In examining the fluorescence quantum yield in the solid state of Compound 22, a spin coat film of the obtained Compound 22 was prepared. The spin coat film was prepared by preparing a THF solution in which the concentration of compound 22 was about 1 mgZO.25 mL, and 0.3 mL of this solution was dropped on a quartz plate placed on a spin coater (Mikasa, 1H-D7), This was prepared by rotating for 60 seconds at lOOOrpm and then further rotating for 20 seconds at 300rpm.

[0075] (4) Measurement of absorption spectrum and fluorescence spectrum

About the obtained spin coat film, while measuring an absorption spectrum using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-3150), a spectrofluorophotometer (manufactured by Hitachi, F45) 00) was used to measure the fluorescence spectrum. Table 2 and Fig. 8 show the measurement results. Table 2 shows the absorption maximum wavelength and the fluorescence maximum wavelength, and FIG. 8 shows the absorption spectrum and the fluorescence spectrum. As shown in Table 2, the absorption spectrum of the spin coat film showed an absorption maximum at 386 nm, and showed a fluorescence maximum at 486 nm when photoexcited at this wavelength. The same measurement was performed on a solution obtained by dissolving Compound 22 in THF (about 1 mgZO. 25 mL). In the solution state, the solution showed an absorption maximum at 371 nm and a fluorescence maximum at 477 nm. In addition, although the absorption spectrum and fluorescence spectrum in the solid state shifted a little longer than the solution state, the shape of the spectrum was almost the same in the solid state and the solution state (see Fig. 5). Further, in order to confirm the effect of introduction of a boron substituent into the side chain, as Comparative Example 1, 5, 5′-bis (dimesitylboryl) 2, 2, 1-bithiophene (compound 23 below) was A spin coat film was prepared in the same manner as described above, and the absorption spectrum and fluorescence spectrum were measured and compared with the spectrum in a solution state dissolved in THF. The results are shown in Fig. 6. As shown in FIG. 5 and FIG. 6, in the fluorescence spectrum, a long wavelength shifted peak corresponding to the excimer emission was observed in the fluorescence spectrum of the compound 23 with respect to the spin coat film. With compound 22, excimer luminescence, which has almost no change in the waveform of the fluorescence spectrum compared with that in THF solution, was not observed. From this, it can be said that Compound 22 can more effectively suppress the interaction between molecules in the solid state (spin coat film).

[Table 2]

Compound 23

[0078] (5) Measurement of fluorescence quantum yield

With respect to the obtained spin coat film, the fluorescence quantum yield (φ) was measured using a quantum yield measuring device (C9920 01, manufactured by Hamamatsu Photonicus). As a result, φ = 0.55 for the spin coat film (see Table 2). This value is a quantum yield sufficient as a luminescent material, and it was confirmed that Compound 22 emits highly efficient light in the visible region in the solid state. Further, as Comparative Example 1, a spin coat film was prepared in the same manner as for Compound 23, and the fluorescence quantum yield Φ was measured to be φ = 0.46 (see Table 2). From this, it is considered that the high-efficiency fluorescence quantum yield obtained with Compound 22 is due to the influence of the boron substituent introduced into the side chain. In other words, the π-electron skeleton of compound 22 is twisted and the three-dimensional structure is firmly fixed, which weakens the intermolecular interaction in the solid state, thereby suppressing quenching.

It is presumed that

[0079] (6) Measurement of cyclic voltammetry

FIG. 7 shows the results of cyclic voltammetry performed on the obtained compound 22. Cyclic voltammetry uses n- Bu N ⁺ PF ⁶ "(0.1 M) as the indicator electrolyte.

Four

Used in THF solution. As a result, it is reversible to E = 2.44V (vs Fc / Fc ⁺ )

1/2

A reduction wave was shown (see Fig. 7). This result indicates that Compound 22 has electron accepting ability.

Example 7

[0080] (1) Synthesis of 3, 5, 5, monotris (dimesitylboryl) 2, 2, monobithiophene

Compound 22 (0.103g, 0.249mmol) and Mes BF (0.346g, 1.29mmol) ether

2

Diisopropylamine (0.18 mL, 1.28 mmol) and n-BuLi (l. 56 M, 0.80 mL, 1.25 mmol) were prepared in ether (5 mL) at 0 ° C. An ether solution of LDA was prepared at 0 ° C. After stirring for 34 hours at room temperature, water (20 mL) was added. The aqueous layer was extracted four times with ether (10 mL), combined with the organic layer, dried over MgSO, and evaporated.

Four

Concentration with a porator gave 0 507 g of crude product. The obtained mixture was separated and purified by silica gel chromatography (hexane: dichloromethane = 5: 1, Rf = 0.30) and GPC (black mouth form), and 0.225 g (0.247 mmol) of 3, 5, 5, -Tris (dimesitylboryl) -2,2'-bithiphene (compound 24 below) was obtained as a yellow-green solid in a yield of 99%. When the melting point of the solid obtained using a micro melting point measuring apparatus (MP-S3, manufactured by Yanaco) was measured, the melting point was 144.2-144.8 ° C. The spectrum data is as follows.

[0081] ^J H NMR (400 MHz, CDC1) δ 1.92 (s, 12H), 1.99 (s, 12H), 2.08 (s, 12H), 2.18 (s

Three

6H), 2.27 (s, 6H), 2.28 (s, 6H), 6.59 (s, 4H), 6.77 (s, 4H), 6.78 (s, 4H), 6.89 (d, J

HH

= 3.6 Hz, 1H), 6.99 (d, J = 3.6 Hz, 1H), 7.31 (s, 1H); ^U B NMR (128 MHz, CDC1

HH S

) δ 70.5 (br) Unit: ppm.

Compound 22 Compound 24

[0083] (2) Spectrum measurement and fluorescence quantum yield measurement

A spin coat film of Compound 24 was prepared in the same manner as in Example 6 (3) above, and the absorption spectrum, fluorescence spectrum and fluorescence quantum yield were in the same manner as in Example 6 (4) and (5) above. The rate was measured. As a result, the spin coat film showed an absorption maximum at 41 lnm and a fluorescence maximum at 509ηm (see Table 2). In the solution state, the absorption maximum was shown at 406 nm and the fluorescence maximum was shown at 480 nm. In addition, as shown in FIG. 8, the fluorescence spectrum shifted slightly longer in the solid state than in the solution state, but the shape of the spectrum was substantially the same. Compared with compound 23 of Comparative Example 1 (see FIG. 6), the fluorescence spectrum in the spin coat film showed a long-wavelength shifted peak corresponding to excimer emission, whereas the fluorescence spectrum was compared with compound 23. In 24, as in the case of Compound 22, the waveform of the fluorescence spectrum was almost unchanged compared to that of the THF solution, and no excimer emission was observed. From this, it can be said that Compound 24 can more effectively suppress the interaction between molecules in the solid state (spin coat film). Also, fireflies on the spin coat film The photon yield Φ was Φ = 0.77, which was very good compared to Comparative Example 1 (φ = 0.46). This value was a good quantum yield, and it was confirmed that Compound 24 exhibited highly efficient light emission in the visible region in the solid state.

Example 8

[0084] (1) Synthesis of 5, 5 'Jib Mouth 3 Dimesitylbolyl 2, 2, Ibithiophene

Compound 22 (1.24 g, 3. OOmmol) and N-bromosuccinimide (NBS) (1.12 g, 6.3 Ommol) were dissolved in a mixed solvent of acetic acid (40 mL) and black mouth form (40 mL), Stir at room temperature for 18 hours. Water (40 mL) was added and the aqueous layer was extracted 3 times with black mouth form (10 mL). The organic layers were combined, washed with saturated aqueous NaHCO (40 mL), dried over Mg SO, and evaporated.

3 2 4

Concentration in one ter yielded 1.89 g of crude product. The resulting mixture was passed through a short column of silica gel (developing solvent: black mouth form) and 1.69 g (2.95 mmol) of 5,5, -dib mouth moe-3 dimesitylboryl 2,2,2 'bitiophene ( The following compound 25) was obtained as a yellow-green solid in a yield of 98%. When the melting point of the solid obtained using a micro melting point measurement apparatus (MP-S3, manufactured by Yanaco) was measured, the melting point was 174.6-174.8 ° C. The spectrum data are as follows.

[0085] 1H NMR (400 MHz, CDC1); δ 2.03 (s, 12H), 2.24 (s, 6H), 6.45 (d, J = 4.0 Hz, l

3 HH

H), 6.61 (d, J = 4.0 Hz, 1H), 6.69 (s, 4H), 6.85 (s, 1H); ¹³ C NMR (100 MHz, CDC

HH

I) δ 21.2, 23.1, 111.9, 113.2, 127.5, 128.2, 129.5, 136.7, 137.1, 139.3, 140.6, 14

Three

1.5, 145.6, 149.3; ⁿ B NMR (128 MHz, CDC1) δ 70.0. Unit: ppm. Anal. Calcd for

Three

C H BBr S: C, 4.57; H, 4.40; N, 0.00. Found: C, 54.30; H, 4.48; N, 0.00.

26 25 2 2

[0086]

Compound 22 Compound 25

(2) Synthesis of 3 dimesitylboryl-1,5,5,1bis (diphenylaminophenol) 1,2,2,1bithiophene

Compound 25 (0. 283g, 0. 494mmol), 4- (diphenylamino) tributylstanl To a solution of benzene (0. 808 g, 1.51 mmol) in THF (15 mL) was added Pd (dba) -CHCl (9.0.

2 3 3 mg, 1.8 mol%) and tri (2-furyl) phosphine (9.7 mg, 8.5 mol%) were added, and the mixture was stirred under an argon atmosphere for 15 hours. The solvent was distilled off under reduced pressure, passed through a short column of silica gel (developing solvent: black mouth form), and purified by silica gel chromatography (hexane: black mouth form = 5: 2, Rf = 0.32). After further separation and purification by GPC (black mouth form), 0.211 g (0.2 34 mmol) of 3-dimesitylboryl-1,5,5,1bis (diphenylaminophenol) 1,2,2, bithiofone (compound 26 below) ) As an orange solid in 47% yield. When the melting point of the solid obtained using a micro melting point measuring apparatus (MP-S3, manufactured by Yanaco) was measured, the melting point was 134.0 to 134.8 ° C. The spectrum data is as follows. Dba represents dibenzylideneacetone.

[0088] ^J H NMR (270 MHz, CDCl) δ 2.08 (s, 12H), 2.20 (s, 6H), 6.68 (s, 4H), 6.74 (d, J

3 H

= 3.6 Hz, IH), 6.80 (d, J = 3.6 Hz, IH), 6.98—7.13 (m, 17H), 7.21-7.30 (m, 10H),

H HH

7.38—7.44 m, 2H); ¹³ C NMR (100 MHz, CDCl) δ 21.2, 23.1, 122.2, 123.0, 123.1,

Three

123.5, 123.7, 124.3, 124.5, 126.4, 126.6, 127.7, 127.9, 128.2, 128.3, 129.26, 129. 29, 129.9, 135.4, 138.8, 140.8, 142.2, 142.6, 144.7, 144.8, 147.1, 147.2, 147.38, 1 47.42 , 148.6; ⁿ B NMR (CDCl) d 68.5. Unit: ppm. HRMS (FAB): 900.3754 (M ⁺ ); C

Three

alcd for C H BN S: 900.3743.

Compound 25 Compound 26

[0090] (3) Spectrum measurement and fluorescence quantum yield measurement

A spin coat film of Compound 26 was prepared in the same manner as in Example 6 (3), and the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield were the same as in Example 6 (4) and (5). The rate was measured. As a result, the spin coat film showed an absorption maximum at 456 nm and a fluorescence maximum at 601 ηm (see Table 2). In the solution state, the absorption maximum was shown at 449 nm and the fluorescence maximum was shown at 600 nm. In addition, the fluorescence quantum yield in the spin coat film is φ = 0.60. It was a favorable value as compared with Comparative Example 1 (= 0.46). This value is also good as a quantum yield, and it was confirmed that Compound 26 exhibits highly efficient light emission in the visible region in the solid state.

[0091] (4) Measurement of cyclic voltammetry

For the obtained Compound 26, cyclic voltammetry was performed in the same manner as in Example 6 (6) above. As a result, a reversible oxidation wave is applied to E = + 0.38V (vs Fc / Fc ⁺ ).

1/2

E =-2. 24V (vs Fc / Fc +) and El / 2 = — 2. 61V (vs Fc / Fc +)

1/2

A reversible reduction wave of the stage was shown (see Fig. 6). This result indicates that Compound 26 has a hole transporting ability and an electron accepting ability.

Example 9

[0092] (1) 3, 4, 1 jib mouth mo 5, 5 "'Synthesis of bis (trimethylsilyl) quaterthiophene

2 To a solution of bromo-5 trimethylsilylthiophene (2.35 g, 10. Ommol) in THF (30 mL;) 78. 78. Add n-BuLi (l. 6M, 9.52 mL, 15.2 mmol) at C; Stirring was continued at C for 2 hours. Triptystannyl chloride (4.13 mL, 4.96 g, 15.2 mmol) was added to the reaction solution, and the temperature was slowly raised to room temperature. To the resulting THF solution of 2 tributylstanl-5 trimethylsilylthiophene, 4, 4, 5, 5, 5, tetrabromo-2,2'-bithiphene (1.86 g, 3. 87 mmol), Pd (dba) -CHC1 (0. 195g, 0. 189m

2 3 3

mol) and trifurylphosphine (0.177 g, 0.76 mmol) were added and refluxed for 10 hours. Water (30 mL) was added to the obtained mixed solution, and then extracted three times with black mouth form. The obtained organic layer was dried over MgSO, filtered, and concentrated under reduced pressure. Sarako, silica gel chromatography

Four

Separation by chromatography (developing solvent: hexane, Rf = 0.40), 1. 07 g (l. 70 mmol) of 5, 5 "'bibis (trimethylsilyl) -3, 4, 4, 1 jib mouth Fen (compound 27 below) was obtained in a yield of 44%.

Compound 27

[0094] (2) 3, 4, 4, bis (dimesitylboryl) 5, 5, ..., bis (trimethylsilyl) quarter Synthesis of thiophene

To a THF solution (10 mL) of compound 27 (0.17 g, 0.27 mmol), 11-: 6111 ^ (1.6 M, 0.38 mL, 0.61 mmol) was added at −78 ° ○, and it was −78. Stirring at C was continued for 1 hour. A THF solution (2 mL) of Me s BF (0. 18 g, 6. 27 mmol) was added to the reaction solution at 78 ° C.

2

The temperature was raised to room temperature. By adding water (10 mL) to the obtained reaction solution and filtering, 0.024 g (0.022 mmol) of 3, 4 ,, -bis (dimesitylboryl) -5, 5, 5,, -bis (tri Methylsilyl) quaterthiophene (compound 28 below) was obtained in a yield of 8%. The spectrum data is as follows.

[0095] ^J H NMR (400 MHz, CDC1) δ 0.19 (s, 18H), 2.05 (s, 24H), 2.20 (s, 12 H), 6.64 (s, 8

H), 6.77 (d, J = 4.0 Hz, 2H), 6.82 (d, J = 4.0 Hz, 2H), 6.91 (s, 2H) Unit: ppm.

Compound 27 Compound 28 Example 10

[0097] (1) Synthesis of 5, 5, ..., bis (diphenylamino) -3, 1-dimesitylboryl quarterthiophene

To a solution of diphenylaminothiophene (528 mg, 2. lmmol) in THF (lOmL) at 78 ° C, add n- BuLi (l. 6M, 1.4 mL, 2.2 mmol) at 78 ° C. After stirring for 20 minutes, the temperature was raised to 0 ° C and stirring was continued for 2 hours. The reaction solution was cooled again to 78 ° C, and tributylstannyl chloride (0.60 mL, 720 mg, 2.2 mmol) was added to the reaction solution, and the temperature was slowly raised to room temperature. The THF solution of the diphenyl (5 tributylstanl 2 chalcamine) thus obtained was added to the 5,5, -dibu-mo-mo 3 dimesitylboryl-2,2, -bithiophene (572.5 mg, 1. OOmmol). , Pd (dba) -CHC1 (20. 7mg, 0.02mmol,

2 3 3

2 mol%) and trifurylphosphine (18.6 mg, 0.08 mmol, 8 mol%) in THF (15 mL) were added by Ca-yura, and the reaction solution was refluxed for 14 hours. Water (40 mL) was added to the mixed solution, and then extracted three times with black mouth form. The resulting organic layer was dried over Na SO and filtered

twenty four

Then, it concentrated under reduced pressure. Furthermore, silica gel chromatography (developing solvent: hexane Z . : Hemp ^_0/0

¾τ¾ (οε 呦 ^^ Stop) Bee ^ ー₍ ζ 'ζ

ε-(/

'V-

5 m

4-yo OH / practice ρ_; ¾ ^o ^ uo £ ^ m ^

9) Be / fi

ε g

Cii l (% \ ^om Z 'louiuieoo Ό' ^ Z 9) lOHO- (^ qp) Pd (louiuios Ό

ε-¾ΰ ΐ- _{ g 'g,: 缀 ^ (rag) JH, ¾¾ΠΠ 荷 ¾ 瀚缀缀ェェ-O) bebe-be ^ / ^

ifH— ίί, one. · Ηπϋ ¾6)> ^ w (° ^mm oQ

-, Ko 5

( ^ra ) Λί ^-^ Ο) (louiuix 8 Ό '3ra66S) bebe> — E— / fi, /

₍ Ζ 'Ζ-

-S-(/ / / 1) ー_{ 9 '9 (Z) [0010]

l Z SI 2

• 2 82 "2T6: S N9 HD Joj popo Ζ882" 2ΐ6: (8Vd) S

HH HH

H: (HS 's) ΐ6 · 9' (HZ ' ^Z H 0 · = f' P) ZS'9 '(HZ' ^Z H 0 · = f 'Ρ) 8Γ9' (Hf 's) 69 • 9' (H9 ^<s ) OZ'Z '{HZ \ ^<s ) 0Γ2 9 (\ DQD' ^z 00,) 匪 Η _τ · 0 _ο 0 0ΐ- 0 · 00ΐ '[8600]

. ^? , Ciiio) Stop ^ ^ ¾ Whip o) Bee ^ — ^ — ^^ ^. , ⁰ / osz ¾τ¾

(6S 呦 ^ ban)

_{ ε- é o

_<{< 9 'QO) (louiui9 ^ _O ) Srai89, 鑭 (SO = JH Ί · £ = ^ ^ ^

L9 Z £ / 900ZdT / 13d 8ε Ϊ69Ζ.0 / .00Ζ OAV (1) () () word) (heavy () p ΰ 6S9 size 9 OSυΐοΐο fHHρH N HsssZ---<----.

9ε H.] ΐο

Sno

1) () () word) (heavy () p ΰ∞ 9 inch 6999 OSυwno fΓHHρH N HsssZ--------. • 2T2S S9: S 9 HD ^ po o ^)

S22S S9: (9VH) SH 'd: -g'sg p (\ 3Q3) Awakening 9 _π : (· 8 ΐ' Γ9 ΐ 'L'Zf ΐ

'Z ST

'S ST' Z ^ Zl '0 "821' β'ΣΖΙ Ί'9ΖΙ '9" 92T' VZZ 'VIZ' 0'ΙΖ '8 2' S S Ρ ODOD

ΗΗ

) One _εΐ- (HZ ^<s ) 06 ・ 9 '(HZ ^<s ) 88 ・ 9' (Ηΐ '^ Η ε = f' Ρ) S8'9 '(Hf' s) S9'9 '( Ηΐ

HH

^<s ) 9S'9 '(HI' ZH YZ = f 'P) If 9' (HS 's) 62 "2' (HS 's) 82"2' (H9 ^<s ) 6Γ2 '(H 9 ^<s ) LVZ '(HZl ^<s ) 60' (Η 9 ^<s ) 96 · ΐ 9 (OQD ^<Z H 00,) HNH _T :. 89Ϊ-Ζ9Ϊ dm [Ζ0Ϊ0]

-

'QO) (louiui92

'1: 01 = Be

(m n ^ wm ^ osm ^ ^ ^ .: · ηί¾ times ø, be

(Ί ^ 09)> ^^) ¾¾ ^ ¾ί. · Η D conversion 9ε. os n ^ra s) Bee Aj¾ (loraraoεε3rao 9) Od ¾¾Q ¥ (% T ^OUI 8

ε gg

^{Ό, § ^ 9 ΌΙ) lOHO-} (Bqp), (i strokes ₀ -. _Z 'SragsS)邈base ci ^ ^,, (I ^ora Ra_〇_G Ό' 3 ^ 98) base E ^ one 'Z - Λ ^ (^ Λ ^^^-£-¾- _{ 9 '9

¾ίί ^) Be ^ ^ ₍ ζ 'ζ--ε-- _{ 9' 9 {) [9010]

• S 22 "99S: S9 Η DP ^ FD n) S822" 99S: (8Vd) S HH 'radd: South · ο · 69 p (i-α) HN 9 _π q) o'6w' z ^ 'v 'v Wz' 6 · 8ει 'v' ζ-m '8 · εει' 8 · οει 'IS'SSI' srssi

'οτζ i' ιτζ 'ζ'ΐζ p (\ DQD) ^ nn _εΐ ' (HS 'ZH τι' ρ) 9s'z '{ηζ' ^Ζ Η Z'L 'Ρ) \ ΥΙ'{' ^ζ

ΗΗ

Η Z'L 'Ρ) WL' (HZ ^<s ) WL '(Ηΐ ZVL' (ΗΖ ' ^Ζ Η = f' Ρ) 68 9 '(Ηΐ' ^ Η =

L9 Z £ / 900ZdT / 13d 0 Ϊ69Ζ.0 / .00Ζ OAV

[0109] (5) Spectrum measurement and fluorescence quantum yield measurement

Spin coat films of compounds 29 to 32 were prepared in the same manner as in Example 6 (3) above, and the absorption spectrum, fluorescence spectrum, and fluorescence amount were the same as in Example 6 (4) and (5) above. The child yield was measured. The results are shown in Table 3 and FIGS. As is clear from Table 3 and Figures 9 to 12, all of compounds 29 to 32 have large differences in absorption maximum wavelength of absorption spectrum and maximum fluorescence wavelength of fluorescence spectrum between film (that is, solid state) and solution state. It was almost the same, and the shape of the spectrum was almost the same. In addition, the quantum yield was strong with no significant difference between the solid state and the solution state. These results indicate that these compounds have almost the same environment in the solid state as in the dilute solution state, and it can be said that the interaction between molecules is effectively suppressed. On the other hand, Compound 29, which has a structure consisting of four thiophene forces, has an absorption maximum of 465 nm (solution 479 nm (solid)), and a fluorescence peak when excited at these wavelengths is nearly 200 nm. A fluorescence maximum was observed around 660, that is, in the red region with a tassel shift, which means that this compound absorbs blue light and emits red light. The compound that shows high quantum yield is limited due to the low band gap theory, but compound 29 has a quantum yield of 0 even in the solid state. The value was relatively high at 30. From these points, the usefulness of Compound 29 is high.

[0110] [Table 3] compound

31 (in THF) 415 543 0.91

(film) 425 554 0.87

32 (in THF) 384 511 0.93

(film) 385 519 0.83

"Only the Jon ^ t absorption m ^ dma are

^{longest absorption madma. c Ab ^ iute} pan um yield detamined by a calibrabwl integrating sphere syst «n,

Needless to say, the present invention is not limited to the above-described embodiment, and can be implemented in various modes as long as it belongs to the technical scope of the present invention.

[0112] This application is Japanese Patent Application No. 2005-362944 filed on December 16, 2005, February 2006, Japanese Patent Application No. 2006-052613, August 2006 filed on February 28, 2006 2 Japanese Patent Application No. 2006-224646, filed on the 1st, is the basis of the priority claim, and the entire contents thereof are incorporated herein by reference. Industrial applicability

[0113] The present invention can be used in the field of organic electronics such as organic EL and organic lasers.

Claims

An organic boron π-electron compound represented by the following formula (1), wherein two boron substituents are introduced at the para position in benzene or substituted benzene.

[Chemical 1]

(However, ΑΓΊ, benzene or substituted benzene,

R ¹ , R ² , R ³ and R ⁴ are each independently phenyl, substituted phenyl, mesityl, substituted mesityl, 2,6-xylyl, substituted 2,6-xylyl, orthotolyl, substituted Lutotolyl group, 2, 4, 6-triisopropyl group, substituted 2, 4, 6-triisopropyl group, 2, 4, 6 —tri-t-butylphenol group, substituted 2,4,6-tri-t-butylphenol 2, 4, 6-tris (trifluoromethyl) phenol group, substituted 2,4,6-tris (trifluoromethyl) phenol group, 2,6-dialkylphenol group, Substituted 2,6-dialkylphenol, 2,4,6-trialkylphenol, substituted 2,4,6-trialkylphenol, 2,6-diarylphenol, substituted 2,6 —Daryl reel group, 2, 4, 6— 卜 -aryl aryl group, substituted 2, 4, 6-triaryl phenol group, chael group, substituted chael group, furyl group, Substituted furyl group, pyrrolyl group, substituted pyrrolyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl group, anthryl group, substituted anthryl group, phenanthryl group, substituted phenanthryl group, pyrenyl group, and substituted pyrenyl group One kind selected from the group,

π ¹ is a divalent group such as jetulbenzene, substituted jeturbenzene, dibulene benzene, substituted dibulenebenzene, benzene, substituted benzene, thiophene, substituted thiophene, pyrrole, substituted pyrrole, furan, substituted furan, pyridine, substituted pyridine , Naphthalene, substituted naphthalene, anthracene, substituted anthracene, phenanthrene, substituted phenanthrene, oligoreel group, substituted oligoreel group, oligoheteroaryl group, substituted oligoheteroaryl group, _α , ω-jetul oligoreel group, α, _ω — Tulle oligo hetero Are, one selected from the group consisting of α, ω-dibule oligomer reel group, ex, _ω -dibule heteroaryl group,

兀² and 兀³ are each independently a monovalent group such as phenylacetylene, substituted phenylacetylene, styryl, substituted styryl, heteroarylacetylene, substituted heteroarylacetylene, heteroarylbule group, substituted heteroaryl Aryl butyl group, phenyl group, substituted phenyl group, chael, substituted chael, pyrrolyl, substituted pyrrolyl, furyl group, substituted furyl group, pyridyl group, substituted pyridyl group, naphthyl group, substituted naphthyl, anthryl Group, substituted anthryl group, phenanthryl group, substituted phenanthryl group, oligoreel group, substituted oligoaryl group, oligoheteroaryl group, substituted oligoheteroaryl group, oligoreyl group, substituted oligoheteroaryl group Selected from the group consisting of oligoarylbule group and substituted oligoheteroarylbule group One kind,

π ¹ and π ² are introduced at the Ar ¹ 〖para position,

n is a value from 0 to 400)

[2] The organoboron π-electron compound according to claim 1, represented by the following formula (2):

[Chemical 2]

[3] The organoboron π-electron compound according to claim 1, represented by the following formula (3):

[Chemical 3]

[4] The organoboron π-electron compound according to any one of claims 1 to 3, wherein η is 0 or 1 [5] The organoboron π-electron compound according to any one of claims 1 to 4, which is used as a luminescent material.

[6] A synthetic intermediate of an organic boron π-electron compound represented by the following formula (4), in which two boron substituents are introduced at the para position in benzene or substituted benzene.

[Chemical 4]

(However, ΑιΠ or benzene or substituted benzene,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a phenyl group, a substituted phenol group, a mesityl group, a substituted mesityl group, a 2,6-xylyl group, a substituted 2,6-xylyl group, or orthotolyl. Group, substituted orthotolyl group, 2, 4, 6-triisopropyl group, substituted 2, 4, 6-triisopropyl group, 2, 4, 6-tri-t-butylphenol group, substituted 2, 4, 6-tri t-butylphenol group, 2, 4, 6-tris (trifluoromethyl) phenol group, substituted 2,4,6-tris (trifluoromethyl) phenol group, 2,6-dialkylphenol -Groups, substituted 2,6-dialkylphenol groups, 2,4,6-trialkylphenol groups, substituted 2,4,6-trialkylphenol groups, 2,6-diarylphenol groups, Substituted 2,6-diarylphenol, 2,4,6-triarylphenyl, substituted 2,4,6-triarylphenol, chael, substituted chael, furyl, Replace Furyl, pyrrolyl, substituted pyrrolyl, pyr

It is one selected from the group consisting of a dil group, a substituted pyridyl group, a naphthyl group, a substituted naphthyl group, an anthryl group, a substituted anthryl group, a phenanthryl group, a substituted phenanthryl group, a pyrenyl group, and a substituted pyrenyl group.

R ⁹ and R ^1G each independently represent an etulyl group, a trialkylsilylethyl group, an alkyldiarylsilylethyl group, a dialkylarylsilylethyl group, a triarylsilylethyl group, a trialkylstanle-tulet group, an alkyldialkyl group, Aryl Stan Etul, Dialkylarylstanle-Luture, Triarylstanle-Luetyl, Aryletul, Substituted Aryletul, Oligoreletul, Substituted Oligorerutinyl, Monovalent Heterocyclic Ethynyl , Substituted monovalent heterocyclic ethynyl group, monovalent oligoheterocyclic ether group, monovalent substituted oligoheterocyclic ether group, substituted ether group, arylylbulu group, substituted arylylbulu group, oligoarylbull group, substituted oligo Aryl vinyl group, monovalent heterocyclic vinyl group, substituted monovalent heterocyclic vinyl group, monovalent oligo heterocyclic vinyl group, monovalent substituted oligo heterocyclic vinyl group, aryl group, substituted aryl group, oligo reel group Substituted oligoaryl group, monovalent heterocyclic group, monovalent substituted heterocyclic group, monovalent oligo heterocyclic group, monovalent substituted oligo heterocyclic group, Luke vinyl group, a substituted metalated Bulle group, metallation Ariru group, a substituted metalated Ariru group, metalated Origoariru group

, Substituted metal oligomer oligoaryl group, monovalent metalated heterocyclic group, monovalent substituted metalated heterocyclic group, monovalent metalated oligoheterocyclic group, monovalent substituted metalated oligoheterocyclic group, halogenated aryl Group, halogenated aryl group, halogenated aryl group, substituted halogenated group, substituted halogenated aryl group, substituted halogenated aryl group, halogenated oligoaryl group, halogenated oligomeric group, nod group Rogenized oligoreyl group, substituted halogenated oligoreel group, substituted halogenated oligoreeltulle group, substituted nonogenated oligoreelbule group, monovalent halogenated heterocyclic group, monovalent halogenated heterocyclic group Ethynyl group, monovalent halogenated heterocyclic vinyl group, monovalent substituted halogenated heterocyclic group, 1 Substituted halogeni ハロゲン heterocyclic ether groups, monovalent substituted halogeni 匕 heterocyclic buyl groups, monovalent halogenated oligoheterocyclic groups, monovalent halogenated oligoheterocyclic ethynyl groups, monovalent halogenooligoheteroheterocycles (Bulu group, monovalent substituted halogeno-oligoheterocyclic group, monovalent substituted halogeno-oligoheterocyclic ethynyl group, and monovalent substituted halogeno-oligoheterocyclic buyl group) 7. The synthetic intermediate of an organic boron π-electron compound according to claim 6, represented by the following formula (5), wherein two boron substituents are introduced at the para position in benzene or substituted benzene.

[Chemical 5]

(However, R and R are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, a trialkylstanl group, an alkyldiarylstanl group, or a dialkyl. Aryl reel group, triaryl stall group, metallized aryl group, substituted metallized aryl group, metal oligomer oligo reel group, substituted metal oligomer oligomer group, monovalent metallized heterocyclic group, monovalent substituted meta Alkylated heterocyclic group, monovalent metalated oligoheterocyclic group, monovalent substituted metallated oligoheterocyclic group, aryl group, substituted aryl group, oligo reel group, substituted oligo reel group, monovalent heterocyclic group, monovalent group Substituted heterocyclic groups, monovalent oligoheterocyclic groups, monovalent substituted oligoheterocyclic groups, halogenated aryl groups, substituted halogenated groups Reel group, halogenated oligo reel group, substituted halogenated oligo reel group, monovalent halogenated heterocyclic group, monovalent substituted halogenated heterocyclic group, monovalent halogenated oligoheterocyclic group, and monovalent substituted halogen Oligo-heteroheterocyclic group is one selected from the group

7. The synthetic intermediate of an organic boron π-electron compound according to claim 6, represented by the following formula (6), wherein two boron substituents are introduced at the para position into benzene or substituted benzene.

[Chemical 6]

(However, R "and R ¹⁴ are each independently a hydrogen atom, a trialkylsilyl group, an alkyldiarylsilyl group, a dialkylarylsilyl group, a triarylsilyl group, a trialkylstanl group, or an alkyldiarylstanl group. , Dialkyl aryl ester group, tri Arylene group, metallized aryl group, substituted metallized aryl group, metal oligomer oligo reel group, substituted metal oligomer oligo reel group, monovalent metallized heterocyclic group, monovalent substituted metallized heterocyclic group, monovalent Metalated oligoheterocyclic group, monovalent substituted metallated oligoheterocyclic group, aryl group, substituted aryl group, oligo reel group, substituted oligo reel group, monovalent heterocyclic group, monovalent substituted heterocyclic group, monovalent Oligo heterocyclic group, monovalent substituted oligo heterocyclic group, halogen aryl group, substituted halogen aryl group, halogenated oligo reel group, substituted halogenated oligo reel group, monovalent halogenated heterocyclic group, monovalent A substituted halogenated heterocyclic group, a monovalent halogenated oligoheterocyclic group, and a monovalent substituted halogenated oligoheterocyclic group.

[9] An organoboron π-electron compound represented by the following formula (7).

[Chemical 7]

(In the formula (7), R ¹ and R ² are each independently a phenyl group, an orthoalkylphenyl group, a substituted orthoalkylphenyl group, a 2,6-dialkylphenol group, a substituted 2 group, , 6-dialkylphenol, 2, 4, 6-trialkylphenol, substituted 2, 4, 6-trialkylphenol, 2, 6-diarylphenol, substituted 2, 6— Diarylphenol, 2, 4, 6-triarylphenol, substituted 2, 4, 6-triarylphenol, chael, substituted chael, furyl, substituted furyl, pyrrolyl 1 group selected from the group consisting of a group, a substituted pyrrolyl group, a pyridyl group, a substituted pyridyl group, a naphthyl group, a substituted naphthyl group, an anthryl group, a substituted anthryl group, a phenanthryl group, a substituted phenanthryl group, a pyrenyl group, and a substituted pyrenyl group And

R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkylthio group, a fluoroalkyl group, an aryl group, or a substituted aryl. Group, aryloxy group, aryloxy group, arylalkyl group, aryloxy group, arylalkylthio group, monovalent heterocyclic group, monovalent substituted complex A cyclic group, an alkyl group, a substituted alkenyl group, an alkyl group, a substituted alkynyl group, an aryl group, an amino group, a substituted amino group, an azo group, a carboxyl group, an acyl group, an alkoxycarbonyl group, a formyl group, Nitro group, cyano group, silyl group, substituted silyl group, phosphino group, substituted phosphino group, silyloxy group, substituted silyloxy group, arylsulfuroxy group, alkylsulfonyloxy group, boryl group, substituted boryl group, and neuron nuclear power One kind selected from the group

1 is a value from 1 to 20, m is a value from 0 to 20, and n is a value from 1 to 100. )

[10] The organoboron according to claim 9, wherein R ¹ and R ² are each independently a 2,4,6-trialkylphenyl group or a substituted 2,4,6-trialkylphenyl group. π-electron compound.

[11] The organoboron π-electron compound according to claim 9 or 10, which is a group represented by the following formula (8): at least one of R ⁵ and R ⁶ .

[Chemical 8]

-(8)

R ⁸

[12] The organoboron π-electron compound according to claim 9 or 10, which is a group represented by the following formula (9): at least one of R ⁵ and R ⁶ . [Chemical 9]

[13] The organoboron π-electron compound according to any one of claims 9 to 12, wherein R ³ and R ⁴ are hydrogen atoms.

[14] The organoboron π-electron compound according to any one of claims 9 to 13, wherein 1 and m are 1, and n is 1 or 2.

[15] The organic boron π electron according to claim 9 or 10, wherein 1, m and η are all 1, and R ⁵ and R ⁶ are an aryl group, a substituted aryl group or a monovalent substituted heterocyclic group. Compounds.

16. The organoboron π-electron compound according to claim 15, wherein the aryl group is a phenyl group, the substituted aryl group is a substituted full group, and the substituted heterocyclic group is a substituted chenyl group.

[17] The organoboron π-electron compound according to claim 16, wherein the substituted chenyl group is a diarylaminochel group.

[18] A luminescent material comprising the organoboron π-electron compound according to any one of claims 9 to 17.

[19] A charge transport material comprising the organoboron π-electron compound according to any one of claims 9 to 17.