JP2011184430A - Boron-containing compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new boron-containing compound which is useful as a light emitting material etc., for organic EL elements or N-type semiconductors, a boron-containing polymer obtained using the compound, and a method for the producing the boron-containing compound, which enables low-cost production of the boron-containing compound and the boron-containing polymer. <P>SOLUTION: There is provided a light emitting material containing the boron-containing compound of formula (1), which has a boron atom and a double bond (in the formula, dotted arcs show that ring structures are formed together with part of a skeleton moiety connecting a boron atom and a nitrogen atom. The dotted line portion in the skeleton moiety connecting the boron atom and the nitrogen atom shows that at least a pair of atoms is bonded by a double bond, and the double bond may conjugate with the ring structure. The arrow from the nitrogen atom to the boron atom shows that the nitrogen atom coordinates to the boron atom. X<SP>1</SP>, X<SP>2</SP>, R<SP>1</SP>and R<SP>2</SP>each represents a hydrogen atom or a monovalent substitutent). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a boron-containing compound and a method for producing the same. More specifically, the present invention relates to a boron-containing compound that can be suitably used as a functional electronic element material such as a light emitting device such as an organic EL element or a material of an organic semiconductor, and a method for producing the same.

An organoboron compound having a boron atom in its structure is attracting attention as a functional electronic device material because of electronic characteristics resulting from an electronic state in the molecular orbital of the boron atom. For example, it is expected as a material for an organic EL (electroluminescence) element and a material for an N-type semiconductor that require characteristics such as electron acceptability. In particular, since organic EL elements have various excellent characteristics as displays, development of materials capable of realizing further higher performance has been actively promoted. In addition, development of practical use of a HOILED (hybrid organic-inorganic light-emitting diode) element using an inorganic material for the hole layer and the electron transport layer has been underway, and development of a suitable material has been awaited. The HOILED element has an advantage that it has higher resistance to oxygen and water than the organic EL element by being hybridized. Thus, the necessity of strictly sealing each layer inside the element can be reduced, so that labor during manufacturing can be reduced, production cost can be reduced, and various excellent characteristics as a display can be obtained.

Several examples of organoboron compounds that have been studied for use in organic EL devices have been known so far, but most of them have been limited to those in which three aryl groups are bonded on a boron atom. It is difficult for organoboron compounds to have a stable structure due to their electronic characteristics, and therefore there are currently only a limited number of organic boron compounds that can be used for electronic materials. In order to utilize such organoboron compounds as materials for next-generation functional electronic devices, various new compounds that can be handled stably are developed while exhibiting excellent unique properties derived from boron atoms. It was what I wanted.

As a conventional organic boron-containing compound, it is disclosed that an organic boron compound having a structure in which a vinyl group is bonded to boron is used as a material for an organic EL element (for example, see Patent Document 1). In addition, it is disclosed that an organic boron π-electron compound having a specific structure is used as an electron transport material (see, for example, Patent Document 2), and for organic compounds containing dimesitylboryl-substituted thienyltriazole, etc. It has actually been shown that the LUMO energy level of the compound is low (see Non-Patent Document 1, for example).

Furthermore, as an organic boron-containing compound that has been studied for use as a material for an organic EL device, a boron compound having a coordination bond in the molecule has been developed in addition to the above-described structure. An organic EL element material that is an organic boron-containing compound having a specific structure and containing an element having a counter electron and capable of coordinating with boron has been disclosed (for example, see Patent Document 3). In addition, an organic electroluminescent element containing an organic boron-containing compound having a specific structure having a structure in which a nitrogen atom is coordinated to a boron atom in the molecule is disclosed (for example, see Patent Document 4). In addition, it is an organic EL element material (for example, refer to Patent Document 5), which is an organic boron-containing compound having a specific structure having 3 to 15 boron atoms in the molecule, or an organic boron-containing compound having a specific structure. An organic EL element material (for example, see Patent Document 6) is disclosed.

By the way, as for the HOILED element, fluorene and polyfluorene derivatives in which various derivatives are known in the field of material chemistry have been studied. For example, a HOILED element using a fluorene derivative as a light emitting layer (see, for example, Non-Patent Document 2), an anode and a cathode, one or more organic compound layers sandwiched between the anode and the cathode, an anode, Disclosed is an organic thin film light emitting device having at least one metal oxide thin film between an organic compound layer and between a cathode and an organic compound layer, and the organic compound layer is composed of a polyfluorene derivative. (For example, refer to Patent Document 7).

JP 2009-155325 A (1-2, 218-220) International Publication No. 2006/070817 (Page 1-2) International Publication No. 2005/062676 (Page 1-5) JP 2007-35791 A (page 1-2) JP 2000-290645 A (page 1-2) International Publication No. 2005/062675 (pages 36-37) JP 2007-53286 A (1-2, 13-14)

Atsushi Wakamiya, two others, “Angewandte Chemie International Edition”, 2006, 45, p. 3170-3173 Katsyuuki Morii, 6 others, “Applied Physics Letters”, 2006, Vol. 89, p. 183510-1 to 183510-3

Organoboron compounds originate from the electronic state of the boron atom, where the boron atom has a vacant orbital in its molecular orbital, thereby lowering the energy levels of the highest occupied orbital (HOMO) and lowest vacant orbital (LUMO). Has characteristics. In particular, due to the low energy level of LUMO, applications as organic EL element materials and N-type semiconductor materials are expected as described above. For example, a general configuration of a low molecular organic EL element, that is, an anode formed from a transparent electrode, a hole (hole) transport layer, a light emitting layer, an electron transport layer, a cathode formed from Mg, Al, Ca, etc. In the structure, if a material having a low LUMO energy level is used for the electron transport layer and the light emitting layer, the performance as a functional electronic element is improved. In addition, light emission in the general configuration of the polymer organic EL, that is, the anode formed from the transparent electrode, the hole (hole) transport layer, the light emitting / electron transport layer, the cathode formed from Ca, Ba, etc. If a material having a low LUMO energy level is used for the cum-electron transport layer, the performance as a functional electronic device is improved. Regarding the HOILED element, the LUMO of fluorene and polyfluorene derivatives that have been studied in the past is high, and is actually unsuitable for the HOILED element, and stable light emission cannot be obtained. As an alternative material, LUMO has a low LUMO, and further development of an excellent material as a light emitting material is expected.
On the other hand, the problem with organic boron compounds is that there are few stable compounds as the boron atoms have vacant orbitals. If the energy level of HOMO and LUMO can be lowered while being a stable compound, it is useful for use as a functional electronic device material. Increasing the variation of such compounds has great technical significance when the compound itself is used as an element material in the field of organic EL elements, N-type semiconductors, HOILED elements, or when a polymer prepared from the compound is used. There is.

In general, in order to obtain a stable structure in an organic boron compound, a structure in which a so-called bulky bulky group is bonded to a boron atom may be used. In the prior art, organic boron compounds have many structures in which three aryl groups are bonded to a boron atom because haloboron compounds such as precursors such as fluorodimesitylborane and 5-bromodibenzoborol are stable. This is because the substituent on the boron has a bulky structure in order to obtain the properties. Moreover, although the organic boron containing compound which has a vinyl group as a substituent is synthesize | combined in patent document 1, it is necessary to use an expensive palladium catalyst in the manufacturing method of such a boron containing compound. In these organoboron compounds, the structure of the compound which can be manufactured and the polymer which uses this compound as a raw material will be restricted. In each of Patent Documents 3 and 4, an element capable of coordinating and bonding with a boron atom is coordinated to the boron atom in the molecule, and an organic boron-containing compound having a specific structure is synthesized. In this method for producing a boron-containing compound, it is only possible to produce a compound having a very limited structure, and it is difficult to produce a polymer using the compound as a raw material. It may be difficult. Moreover, the boron containing compound of patent document 5 is a thing to a 15-mer, and it is not disclosed about the multimer beyond it. Further, also in Patent Document 6, what can be produced by the described method for producing a boron-containing compound is a compound having a limited structure.
In the future development of organic EL elements, N-type semiconductors, HOILED elements, etc., various characteristics are required, and it is required to prepare various polymers from such compounds. Here, in Patent Documents 2 to 6 described above, it is disclosed that the organic boron-containing compounds described therein are used as an electron transport material, a hole blocking material, and a host compound in a light emitting layer. If a compound having a low LUMO and a high light emission yield can be synthesized, it can be suitably used as a light emitting material such as an organic EL device or a HOILED device.
In order to design a material that can meet such requirements, it is preferable that various novel organoboron compounds can be prepared and organoboron compound derivatives having various structures can be easily obtained at low cost. For example, if the type of a substituent in a boron atom can be changed selectively and with a high degree of freedom, it is extremely beneficial in the development of a new organic EL element and a new organic semiconductor.
Further, if a pseudo-fluorene compound group having a low LUMO can be synthesized in place of fluorene and polyfluorene which have been studied as materials for HOILED elements, the practical application of HOILED elements may greatly advance.

The present invention has been made in view of the above situation, and is useful as an organic EL element, a light emitting material for an N-type semiconductor, and the like, a novel boron-containing compound, a boron-containing polymer obtained using the compound, and boron It aims at providing the manufacturing method of the boron containing compound which makes it possible to manufacture a containing compound and a boron containing polymer cheaply.

The present inventors have made various studies on new boron-containing compounds and new methods for producing various boron-containing compounds. In order to make the boron-containing compounds stable, nitrogen is added to the boron atom. It was noticed that the atoms should have a coordinated structure. Further, a boron-containing specific structure in which a bromine atom or an iodine atom is bonded to a boron atom, a double bond is formed in a skeleton having a boron atom and a nitrogen atom, and the skeleton forms a part of at least two ring structures Although the compound is a stable compound, it has been found that the compound is a useful compound that can lower the energy levels of HOMO and LUMO, and the inventors have conceived that the above problems can be solved brilliantly. Also, a compound having a specific structure having a nitrogen atom and two ring structures in the structure and further having at least one double bond is reacted with a brominated or iodinated boron-containing compound having a specific structure. Thus, it was found that various boron-containing compounds having a structure in which a bromine atom or an iodine atom is bonded to a boron atom as a substituent and a nitrogen atom is coordinated to the boron atom can be produced without using an expensive palladium catalyst. . Furthermore, the bromine atom or iodine atom bonded to the boron atom of such a boron-containing compound can be converted into another atom or atomic group, and thereby boron-containing compounds having various structures that have been difficult to produce by conventional methods. It has been found that a boron-containing polymer having various structures can be produced by using a boron-containing compound obtained in this manner and that the boron-containing compound thus obtained has been achieved.
In addition, in the field of HOILED elements and the like, it is conceivable to introduce boron atoms into the molecule as means for lowering LUMO instead of fluorene and polyfluorene that have been studied so far. It was also found that by introducing a boron atom into the group, a pseudofluorene compound group having an isoelectronic structure such as fluorene or the like and having a low LUMO can be synthesized. Then, it was found that the value of the emission quantum yield of these compounds is related to the suitability as a functional electronic device material, and by specifying the range, stable emission characteristics can be obtained, and organic It has been conceived that it becomes a boron-containing compound that can be particularly suitably used as a light-emitting material constituting a light-emitting layer of an HOILED element as a light-emitting material constituting a light-emitting layer of an EL element or the like.
Thus, one of the preferable forms of the present invention is a compound in which the emission quantum yield is in a specific range among the boron-containing compounds having a specific structure, and one of the preferable forms of the present invention is Among the boron-containing compounds having a specific structure, a compound having a linear or branched hydrocarbon group or an alicyclic hydrocarbon group as a specific functional group (substituent). In addition, it is also preferable that it is a form which has the component of both of these two preferable forms.

That is, this invention is a luminescent material containing the boron-containing compound which has a boron atom and a double bond, Comprising: The said boron-containing compound is following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent.
The present invention is described in detail below.

The luminescent material of the present invention has the following formula (1):

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent, and includes a boron-containing compound having a structure represented by:
The light emitting material of the present invention can be suitably used as a light emitting material constituting a light emitting layer of an organic EL element or the like, and is not used as a host material of a light emitter, and itself is a light emitter. It is used as

In the above formula (1), the dotted circular arc represents that a ring structure is formed together with a part of the skeleton portion that connects the boron atom and the nitrogen atom. That is, the boron-containing compound represented by the above formula (1) has at least two ring structures in the structure, and in the above formula (1), the skeleton portion connecting the boron atom and the nitrogen atom is It is included as a part.
In the above formula (1), a dotted line part in a skeleton part connecting a boron atom and a nitrogen atom represents that at least one pair of atoms is connected by a double bond, and the double bond is conjugated with a ring structure. Represents a good thing. Among the compounds represented by the formula (1), examples in which the double bond is conjugated to the ring structure include structures having the following formulas (2-1) to (2-4).

In the above formula (1), the arrow from the nitrogen atom to the boron atom represents that the nitrogen atom is coordinated to the boron atom. Here, coordinating means that the nitrogen atom acts on the boron atom in the same manner as the ligand and has a chemical effect, and is a coordinate bond (covalent bond). Or a coordinate bond may not be formed. Preferably, it is a coordinate bond.
In the above formula (1), X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. You may do it. That is, when X ¹ and X ² are hydrogen atoms, in the structure of the boron-containing compound represented by the formula (1), two ring structures having X ¹ and X ² do not have a substituent. In the case where X ¹ and / or X ² is a monovalent substituent, either one of the two ring structures or both have a substituent. In that case, the number of substituents in one ring structure may be one, or two or more.
In the present specification, the substituent means a group including an organic group containing carbon and a group not containing carbon such as a halogen atom and a hydroxy group.

Since the boron-containing compound in the present invention has a low LUMO energy level, it can be suitably used as a material for an organic EL device or a material for an N-type semiconductor. The LUMO energy level of the compound is preferably, for example, 3.0 eV to 5.2 eV. In such a range, when used as a material for an organic EL element or an N-type semiconductor, performance can be sufficiently exhibited. The energy level of LUMO is more preferably 3.2 eV to 5.1 eV, and still more preferably 3.4 eV to 5.0 eV. Particularly preferably, it is 3.6 eV to 5.0 eV.
Note that the LUMO energy level is preferably obtained, for example, as in the examples and comparative examples described later in this specification.

In the above formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent substituent. R ¹ and R ² may be the same or different, but are preferably the same. The R ¹ and R ² are not particularly limited, and for example, a hydrogen atom, an aryl group which may have a substituent, a heterocyclic group, an alkyl group, an alkoxy group, an arylalkoxy group, a silyl group, a hydroxy group , A boryloxy group, an amino group, a halogen atom, a 2,2′-biphenyl group formed by bonding R ¹ and R ² , an optionally substituted oligoaryl group, a monovalent oligoheterocyclic group, Alkylthio group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, azo group, stannyl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy group; methanesulfonate group, ethanesulfonate group, trifluoromethane Alkyl sulfonate groups such as sulfonate groups; benzene sulfonate groups aryl sulfonate groups such as p-toluene sulfonate group; aryl alkyl sulfonate groups such as benzyl sulfonate group; boryl groups such as groups represented by the following formulas (3-1) to (3-4); ) To (3-6) a sulfonium methyl group such as a group; a phosphonium methyl group such as a group represented by the following formula (3-7); a group represented by the following formula (3-8) Examples thereof include phosphonate methyl group; aryl sulfonate group; aldehyde group; acetonitrile group; magnesium halide represented by the following formula (3-9).
In the formula, Me represents a methyl group. Et represents an ethyl group. X represents a halogen atom. R ′ represents an alkyl group, an aryl group, or an arylalkyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tetrahydronaphthyl group, an indenyl group, and an indanyl group. Among these, a phenyl group, a biphenyl group, and a naphthyl group are preferable.
Examples of the heterocyclic group include pyrrolyl, pyridyl, quinolyl, piperidinyl, piperidino, furyl, and thienyl groups. Among these, a pyridyl group and a thienyl group are preferable.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Among these, a bromine atom and an iodine atom are preferable.

As said alkyl group, a C1-C30 linear or branched hydrocarbon group and a C3-C30 alicyclic hydrocarbon group are mentioned. That is, in the luminescent material containing the boron-containing compound represented by the formula (1), R ¹ and R ² in the formula (1) are the same or different, and are linear or branched hydrocarbons having 1 to 30 carbon atoms. A group or an alicyclic hydrocarbon group having 3 to 30 carbon atoms is also one preferred embodiment of the present invention.
Specific examples of the linear hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. .
Specific examples of the branched hydrocarbon group having 1 to 30 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, and isopentyl group.
Specific examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.
Among these, the alkyl group is preferably a methyl group, an ethyl group, an isopropyl group, an isobutyl group, or an octyl group. More preferably, they are a methyl group, an ethyl group, an isobutyl group, and an octyl group.

Examples of the substituent in R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, a halogen atom of an iodine atom; a methyl chloride group, a methyl bromide group, a methyl iodide group, a fluoromethyl group, a difluoromethyl group, Haloalkyl group such as fluoromethyl group; straight chain or branched chain having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group Alkyl group; cyclic alkyl group having 5 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy Straight chain having 1 to 8 carbon atoms such as a group, hexyloxy group, heptyloxy group, octyloxy group, etc. Branched or branched alkoxy group; hydroxy group; thiol group; nitro group; cyano group; amino group; mono- or dialkyl having an alkyl group having 1 to 4 carbon atoms such as methylamino group, ethylamino group, dimethylamino group, and diethylamino group Amino group; amino group such as diphenylamino group and carbazolyl group; acyl group such as acetyl group, propionyl group and butyryl group; 2 to 8 carbon atoms such as vinyl group, 1-propenyl group, allyl group, butenyl group and styryl group An alkynyl group having 2 to 8 carbon atoms such as ethynyl group, 1-propynyl group, propargyl group, phenylacetylinyl; alkenyloxy group such as vinyloxy group, allyloxy group; ethynyloxy group, phenylacetyloxy group, etc. Alkynyloxy group; phenoxy group, naphthoxy group, biphenyloxy group, Aryloxy groups such as pyrenyloxy group; perfluoro groups such as trifluoromethyl group, trifluoromethoxy group, pentafluoroethoxy group and the like, and long-chain perfluoro groups; diphenylboryl group, dimesitylboryl group, bis (perfluorophenyl) boryl Boryl groups such as carbonyl groups; carbonyl groups such as acetyl groups and benzoyl groups; carbonyloxy groups such as acetoxy groups and benzoyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and phenoxycarbonyl groups; methylsulfinyl groups and phenyl A sulfinyl group such as a sulfinyl group; a silyl group such as a trimethylsilyl group, a triisopropylsilyl group, a dimethyl-tert-butylsilyl group, a trimethoxysilyl group, or a triphenylsilyl group; a halogen atom or an alkyl group; Phenyl group, 2,6-xylyl group, mesityl group, duryl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, pyrenyl group, toluyl group, anisyl group, fluorophenyl, which may be substituted with a ruxoxy group, etc. Aryl group such as diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, phenanthrenyl group; thienyl group, furyl group, silacyclopentadienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl group A heterocyclic group such as quinolyl group, quinoxaloyl group, phenanthrolyl group, benzothienyl group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl group, pyrrolyl group, benzoxazolyl group, pyrimidyl group, imidazolyl group; Carboxylic acid ester; Epoxy group; Isocyano group; Cyanate group; Isocyanate group; Thiocyanate group; Isothiocyanate group; Carbamoyl group; N, N- such as N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group A dialkylcarbamoyl group; a formyl group; a nitroso group; a formyloxy group; Note that these groups may be substituted with a halogen atom, an aromatic group, or the like, and these groups may be bonded to each other at an arbitrary position to form a ring.
Among these, as a substituent which the monovalent substituent in R ¹ and R ² has, a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear chain having 1 to 8 carbon atoms. Or a branched alkoxy group, an aryl group, or a haloalkyl group is preferred. More preferred are an ethyl group, an isopropyl group, an octyl group, a fluorine atom, a bromine atom, a vinyl group, an ethynyl group, a diphenylamino group, a diphenylaminophenyl group, and a trifluoromethyl group.

Among the above-mentioned R ¹ and R ² , hydrogen atom, bromine atom, methyl group, ethyl group, isopropyl group, isobutyl group, n-octyl group, phenyl group, 4-methoxyphenyl group, 4-trifluoro A methylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2,2′-biphenyl group, a styryl group, and a diphenylaminophenyl group are more preferable. More preferably, bromine atom, methyl group, ethyl group, isopropyl group, isobutyl group, n-octyl group, phenyl group, 4-methoxyphenyl group, 4-trifluoromethylphenyl group, pentafluorophenyl group, 4-bromophenyl. Group, 2,2′-biphenyl group, styryl group, diphenylaminophenyl group, particularly preferably bromine atom, isopropyl group, isobutyl group, n-octyl group, phenyl group, 4-trifluoromethylphenyl group, penta A fluorophenyl group, a 4-bromophenyl group, a 2,2′-biphenyl group, a styryl group, and a diphenylaminophenyl group;

In the above formula (1), X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of a ring structure. Is not particularly restricted but includes monovalent substituent said are the same as those for the R ¹ and R ^2.

Among these, as X ¹ and X ² , hydrogen atom; halogen atom, carboxyl group, hydroxyl group, thiol group, epoxy group, isocyanate group, amino group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl Group, formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy group and the like; linear or branched chain having 1 to 4 carbon atoms A linear or branched alkyl group having 1 to 4 carbon atoms substituted with a linear alkyl group or the reactive group; a linear or branched alkoxy group having 1 to 8 carbon atoms or substituted with the reactive group A linear or branched alkoxy group having 1 to 8 carbon atoms; an aryl group or an aryl group substituted with the reactive group; an oligoary Group or oligoaryl group substituted with the reactive group; monovalent heterocyclic group or monovalent heterocyclic group substituted with the reactive group; monovalent oligo heterocyclic group or substituted with the reactive group An alkylthio group; an aryloxy group; an arylalkyl group; an arylalkoxy group; an alkenyl group substituted with an alkenyl group or the reactive group; an alkynyl group or the alkylthio group; Alkynyl groups substituted with reactive groups are preferred. More preferably, a hydrogen atom, a bromine atom, an iodine atom, a boryl group, an alkynyl group, an alkenyl group, a formyl group, a stannyl group, a phosphino group, an aryl group, an aryl group substituted with the reactive group, or the reactive group A substituted oligoaryl group, an amino group such as a diphenylamino group, a monovalent heterocyclic group such as a group represented by the following formula (3-10), or a monovalent heterocyclic group substituted with the reactive group , A monovalent oligo heterocyclic group substituted with the reactive group, an alkenyl group, an alkenyl group substituted with the reactive group, an alkynyl group, or an alkynyl group substituted with the reactive group.

In the present invention, X ¹ and X ² in the formula (1) is, among those mentioned above, it is also one of the preferred embodiments of the present invention is a substituent having a reactive group. When X ¹ and X ² are substituents having a reactive group among those described above, examples of such substituents include halogen atoms, carboxyl groups, hydroxyl groups, thiol groups, epoxy groups, isocyanate groups. Group, amino group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl group, formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy A reactive group such as a group; a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the reactive group; a linear or branched chain having 1 to 8 carbon atoms substituted with the reactive group A chain alkoxy group; an aryl group substituted with the reactive group; an oligoaryl group substituted with the reactive group; a monovalent heterocyclic ring substituted with the reactive group ; Monovalent oligo heterocyclic group substituted by a reactive group; an alkenyl group, or an alkenyl group substituted with the reactive group; an alkynyl group substituted with an alkynyl group or the reactive group is preferable. More preferably, a bromine atom, an iodine atom, a boryl group, a formyl group, a stannyl group, a phosphino group, an aryl group substituted with the reactive group, an oligoaryl group substituted with the reactive group, or the reactive group Substituted with a substituted monovalent heterocyclic group, monovalent oligoheterocyclic group substituted with the reactive group, alkenyl group or alkenyl group substituted with the reactive group, alkynyl group or reactive group An alkynyl group. More preferably, a bromine atom, a boryl group, a formyl group, a stannyl group, a phosphino group, an aryl group substituted with the reactive group, an oligoaryl group substituted with the reactive group, or a substituted with the reactive group A monovalent heterocyclic group, a monovalent oligoheterocyclic group substituted with the reactive group, an alkenyl group, an alkenyl group substituted with the reactive group, an alkynyl group, or an alkynyl group substituted with the reactive group It is.
When X ¹ and X ² are substituents having a reactive group, the reactive groups of X ¹ and X ² are different, and one boron-containing compound can be polycondensed alone. Either a combination of groups, or two or more boron-containing compounds represented by the formula (1) are included, and the boron-containing compounds have a combination of reactive groups that can be copolymerized. Or a combination of reactive groups such that one or more boron-containing compounds represented by the formula (1) can be copolymerized with another compound having at least one reactive group By having it, it can be suitably used as a raw material for the polymer.

In the above formula (1), the ring structure formed by the dotted arc and a part of the skeleton part connecting the boron atom and the nitrogen atom is not particularly limited as long as it is a cyclic structure. Examples of the ring to which ¹ is bonded include benzene ring, thiophene ring, benzothiophene ring, thiazole ring, oxazole ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, imidazole ring, pyrazole ring, pyridine ring, pyridazine A ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, and an isoquinoline ring, and these are represented by the following formulas (4-1) to (4-17), respectively. Among these, a benzene ring, a naphthalene ring, and a benzothiophene ring are preferable.

Examples of the ring to which X ² is bonded in Formula (1) include a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a pyrimidine ring, an indole ring, an isoindole ring, and a quinoline ring. , Isoquinoline ring, phenanthridine ring, thiazole ring and oxazole ring. These are respectively represented by the following formulas (5-1) to (5-14). Among these, a pyridine ring, a pyrimidine ring, a quinoline ring, and a phenanthridine ring are preferable. More preferred are a pyridine ring, a pyrimidine ring, and a quinoline ring.

When the boron-containing compound in the present invention is the above formula (1) and X ¹ and / or X ² is a monovalent substituent, the bonding position of X ¹ and / or X ² with respect to the ring structure and the number of bonds are as follows: There is no particular limitation.
In addition, as X ¹ , at least two monovalent substituents are bonded to the ring structure, and one of the monovalent substituents is an optionally substituted boryl group, and the monovalent The form in which the other one of the substituents is a pyridyl group which may have a substituent and the nitrogen atom of the pyridyl group is coordinated to the boron atom of the boryl group is also in the present invention. This is one of the preferred embodiments. That is, in the present invention, the boron-containing compound also has one or more portions having a nitrogen atom coordinated to the boron atom in the structure, which is one of the preferred embodiments of the present invention.

One of the preferred embodiments of the present invention is that the boron-containing compound in the present invention has a structure represented by the above formula (1) and has an emission quantum yield of 20 to 100%. It is. When the emission quantum yield of the boron-containing compound is in such a range, it is possible to obtain sufficiently stable light emission when used as a light-emitting material constituting a light-emitting layer in an organic EL device, a HOILED device, or the like. It becomes. More preferably, it is 30 to 100% as an emission quantum yield, More preferably, it is 40 to 100%. Particularly preferably, it is 50 to 100%, and most preferably 60 to 100%.
In addition, it is suitable to obtain | require the light emission quantum yield as it is performed in the Example and comparative example of this-application specification mentioned later, for example.

Among the boron-containing compounds having the structure represented by the above formula (1), in order to satisfy the emission quantum yield of 20% or more, a structure that prevents π-π stacking interaction between molecules is desirable. . That is, by making the boron bulky, the overlap between molecules is reduced, and a light emission quantum yield of 20% or more can be obtained.

In the present invention, in the above formula (1), at least one of X ¹ and X ² has a structure in which two atoms are connected to the terminal portion by a double bond, and one of the two atoms is It is also a preferred embodiment of the present invention that the substituent has a structure bonded to a ring structure that forms a dotted arc portion with atoms. That is, a boron-containing compound having a boron atom and a double bond, the boron-containing compound is represented by the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² may be the same or different and each represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² may be bonded to the ring structure forming the dotted arc portion. R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent substituent.) At least one of the above X ¹ and X ² has a double bond at the end. One of the two atoms having a structure connected by Boron-containing compounds characterized by having a cyclic structure and bonded structure to form a circular arc portion of the dotted line also constitutes the present invention.

A structure in which two atoms are bonded to the terminal portion by a double bond, and a structure in which one of the two atoms is bonded to a ring structure that forms a dotted arc portion is, that is, X ^In the atomic group constituting ¹ and / or X ² , there are at least two terminal portions of the structure, but of these terminal portions, they are bonded to the ring structure forming the dotted arc portion in the above formula (1). It means that the terminal portion has a structure in which an atom bonded to a ring structure forming a dotted arc portion and an atom adjacent to the atom are connected by a double bond. Examples of such substituents include structures represented by the following formulas (6-1) to (6-2).
In the formulas (6-1) to (6-2), * represents an atom bonded to the ring structure forming the dotted arc portion in the formula (1). Z ¹ , Z ² , Z ³ and Z ⁴ are the same or different and are atoms capable of forming double bonds between Z ¹ and Z ² and between Z ³ and Z ⁴ , respectively. Represents. Wherein (6-1), Y ¹ represents a hydrogen atom or a monovalent organic group, and represents that may be a plurality bonded to Z ² depending on the valence of Z ^2. In the formula (6-2), the dotted arc represents that a ring structure is formed together with the double bond portion formed by Z ³ and Z ⁴ . Y ² represents a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure, and may represent that a plurality of Y ² may be bonded to the ring structure forming the dotted arc portion in the formula (6-2). ing.

In the above formulas (6-1) to (6-2), Z ¹ , Z ² , Z ³ and Z ⁴ are the same or different, and are between Z ¹ and Z ² and between Z ³ and Z ⁴ . Are atoms capable of forming a double bond, preferably a carbon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom. More preferably, they are a carbon atom and a nitrogen atom.

In the above formula (6-1), Y ¹ represents a hydrogen atom or a monovalent organic group, but indicates that it may also be a plurality bonded to Z ² depending on the valence of Z ^2, This, for example, when ^{Z 2} is a nitrogen atom, ^{Y 1} becomes to bind one to ^{Z 2,} when ^{Z 2} is a carbon atom, ^{Y 1} binds two to ^{Z 2} It shows that it will be. When a plurality of Y ¹ are bonded to Z ² , all of Y ¹ may be the same or different. The monovalent organic group is not particularly limited, and examples thereof include those similar to R ¹ and R ² in the above formula (1).

Among these, as Y ¹ , hydrogen atom; halogen atom, carboxyl group, hydroxyl group, thiol group, epoxy group, isocyanate group, amino group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl group, formyl Groups, cyano groups, silyl groups, stannyl groups, boryl groups, phosphino groups, silyloxy groups, arylsulfonyloxy groups, alkylsulfonyloxy groups, etc .; straight-chain or branched alkyl groups having 1 to 4 carbon atoms Or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the reactive group; a linear or branched alkoxy group having 1 to 8 carbon atoms or carbon substituted with the reactive group A linear or branched alkoxy group of 1 to 8; an aryl group or an aryl group substituted with the reactive group; an oligoaryl group or the Oligoaryl group substituted with a reactive group; monovalent heterocyclic group or monovalent heterocyclic group substituted with the reactive group; monovalent oligo heterocyclic group or 1 substituted with the reactive group Alkyl heterocyclic group; alkylthio group; aryloxy group; arylthio group; arylalkyl group; arylalkoxy group; arylalkylthio group; alkenyl group or alkenyl group substituted with the reactive group; alkynyl group or reactive group Alkynyl groups substituted with are preferred. More preferably, a hydrogen atom, a bromine atom, an iodine atom, a boryl group, an alkynyl group, an alkenyl group, a formyl group, a stannyl group, a phosphino group, an aryl group or an aryl group substituted with the reactive group, or the reactive group A substituted oligoaryl group, a monovalent heterocyclic group substituted with the reactive group, a monovalent oligoheterocyclic group substituted with the reactive group, an alkenyl group, or an alkenyl substituted with the reactive group An alkynyl group substituted by a group, an alkynyl group or the reactive group.

In Formula (6-2) above, Y ² represents a hydrogen atom or a monovalent substituent that serves as a substituent of the ring structure, and a plurality of Y ² are present in the ring structure forming the dotted arc portion in Formula (6-2). It represents that they may be combined.
That is, when Y ² is a hydrogen atom, the ring structure having Y ² in the structure represented by formula (6-2) has no substituent, and Y ² is a monovalent group. In the case of a substituent, the ring structure has a substituent. In that case, the number of substituents of the ring structure may be one, or two or more.
Examples of the monovalent substituent include those similar to X ¹ and X ² in the above formula (1). Among these, a group represented by the above formula (3-10), a naphthyl group, phenyl Particularly preferred is a group.

In the present invention, furthermore, both X ¹ and X ² in the above formula (1) have a structure in which two atoms are connected to the terminal portion by a double bond, and one of the two atoms It is also a preferred embodiment of the present invention that the substituent has a structure bonded to a ring structure that forms a dotted arc portion with the atoms. That is, a boron-containing compound having a boron atom and a double bond, the boron-containing compound is represented by the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² may be the same or different and each represents a monovalent substituent that is a substituent of the ring structure, and a plurality of X ¹ and X ² may be bonded to the ring structure forming the dotted arc portion And R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of the above X ¹ and X ² is a double bond at the end. Has a connected structure, one of the two atoms is dotted Boron-containing compounds characterized by having a structure bonded with the ring structure forming an arc portion also constitutes the present invention. Such boron-containing compounds are particularly useful as materials for organic EL devices, N-type semiconductors, and the like because they have particularly high emission quantum yields.

In the above formula (1), each of X ¹ and X ² has a structure in which two atoms are connected to each other by a double bond, and a dotted arc portion is formed by one of the two atoms. As the boron-containing compound having a structure bonded to the ring structure to be formed, the double bond portion composed of atoms bonded to the ring structure forming the dotted arc portion in the above formula (1) is largely. However, the form which does not comprise a ring structure and the form which comprises a part of ring structure are mentioned, Specifically, the form of following formula (1'-1)-(1'-4) is mentioned.
In the formulas (1′-1) to (1′-4), the dotted line portion in the skeleton portion connecting the boron atom and the nitrogen atom, the arrow from the nitrogen atom to the boron atom, and R ¹ and R ² are It is the same as the formula (1). In the formula (1′-1), the dotted arc is the same as the formula (1). In the formulas (1′-2) to (1′-4), the dotted circular arc in contact with a part of the skeleton part connecting the boron atom and the nitrogen atom is the boron atom and the nitrogen atom as in the formula (1). A ring structure is formed together with a part of the skeletal part that connects the two, and a double bond part formed by Z ⁵ and Z ⁶ and / or a double bond part formed by Z ⁷ and Z ⁸ The dotted arc in contact indicates that a ring structure is formed with the corresponding double bond portion. Z ^{5 to} Z ⁸ are the same or different and are the same as Z ^{1 to} Z ⁴ in the above formulas (6-1) to (6-2). Y ³ and Y ⁴ are the same or different and are the same as Y ¹ in the above formula (6-1). Y ⁵ and Y ⁶ are the same or different and are the same as Y ² in the above formula (6-2).

Among these forms, in the above formula (1), is the double bond part formed by the atoms bonded to the ring structure forming the dotted arc part together not having a ring structure? Or a part constituting a part of the ring structure is preferred. That is, it is preferable that it is a form of said Formula (1'-1) and (1'-4).
Such a boron-containing compound represented by the above formula (1′-1) or a boron-containing compound represented by the above formula (1′-4) is also one aspect of the present invention.

In the above formula (1′-1), the dotted circular arc represents that a ring structure is formed together with a part of the skeleton portion connecting the boron atom and the nitrogen atom, as in the formula (1). In the formula (1′-1), the ring structure formed by the dotted arc and a part of the skeleton portion connecting the boron atom and the nitrogen atom is not particularly limited as long as it is a cyclic structure. Examples of the ring to which the group having Y ³ is bonded in -1) include the same rings as those in which X ¹ in Formula (1) is bonded. In addition, examples of the ring to which the group having Y ⁴ is bonded in Formula (1′-1) include the same rings as the ring to which X ² in Formula (1) is bonded.

In the above formulas (1′-2) to (1′-4), the dotted circular arc in contact with a part of the skeleton part connecting the boron atom and the nitrogen atom is the boron atom and nitrogen as in the formula (1). It represents that a ring structure is formed together with a part of the skeleton part connecting the atom, and a double bond part formed by Z ⁵ and Z ⁶ and / or a double bond part formed by Z ⁷ and Z ⁸ A dotted circular arc in contact with represents that a ring structure is formed together with the corresponding double bond portion. That is, the boron-containing compounds represented by the above formulas (1′-2) to (1′-3) have at least three ring structures in the structure, and a skeleton portion that connects a boron atom and a nitrogen atom, and One double bond moiety is included as part of the ring structure. In addition, the boron-containing compound represented by the above formula (1′-4) has at least four ring structures in the structure, and a skeleton portion that connects a boron atom and a nitrogen atom, and two double bond portions Is included as part of the ring structure.

In the above formulas (1′-2) to (1′-4), the dotted arc that is in contact with a part of the skeleton part that connects the boron atom and the nitrogen atom, and the skeleton part that connects the boron atom and the nitrogen atom The ring structure formed by a part is not particularly limited as long as it is a cyclic structure, but the ring to which a group containing a double bond portion formed by Z ⁵ and Z ⁶ is bonded is represented by the formula (1). Examples are the same as the ring to which X ¹ is bonded. In addition, examples of the ring to which a group containing a double bond portion formed by Z ⁷ and Z ⁸ is bonded include the same ring as the ring to which X ² in Formula (1) is bonded.

Further, in the above formulas (1′-2) to (1′-4), they are in contact with the double bond portion formed by Z ⁵ and Z ⁶ and / or the double bond portion formed by Z ⁷ and Z ⁸ . Examples of the ring structure formed by the dotted arc and the corresponding double bond portion include, for example, a ring to which X ¹ in Formula (1) is bonded and X ² in Formula (1) is bonded. The thing similar to the ring which is included is mentioned. In the above formula (1′-4), the double bond portion formed by Z ⁵ and Z ^{6, the} dotted circular arc in contact with the double bond portion formed by Z ⁷ and Z ⁸ , and the double Although there are at least two ring structures formed by the linking moiety, they may be the same or different.

The present invention is also a method for producing a boron-containing compound having a structure represented by the above formula (1), wherein the production method comprises the following formula (I);

(In the formula, a dotted arc indicates that a ring structure is formed together with a part of the skeleton part that connects the hydrogen atom and nitrogen atom. The dotted line in the skeleton part that connects the hydrogen atom and nitrogen atom) The moiety represents that at least one pair of atoms is bonded by a double bond, and the double bond may be conjugated to a ring structure, and X ¹ and X ² may be the same or different and represent a hydrogen atom or a ring And a compound represented by the following formula (II): a monovalent substituent serving as a substituent of the structure may be bonded to a ring structure forming a dotted arc part).

(In formula, Q is the same or different and represents a bromine atom or an iodine atom.) It is also a manufacturing method of the boron containing compound which makes the process with the compound represented by these essential.
According to the method for producing a boron-containing compound of the present invention, a novel boron-containing compound can be produced in a relatively short reaction time without using an expensive catalyst such as a palladium catalyst.

The production method may include other steps as long as it includes a step of reacting the compound represented by the formula (I) with the compound represented by the formula (II). In addition, each of the compound represented by the above formula (I) and the compound represented by the above formula (II) may be a single compound or two or more compounds.
The dotted arc in the above formula (I) means that the compound has at least two ring structures in the structure. Preferred examples ^X 1, ^{X 2} and ring structures in the above formula (I) are the same as ^X 1, ^{X 2} and ring structures in the above formula (1).

When the compound represented by the above formula (I) is reacted with the compound represented by the above formula (II), it is represented by the formula (II) with respect to 1 mol of the compound represented by the formula (I). It is preferable to use 1 mol to 10 mol of the compound. More preferably, it is 1 mol-7 mol, and it is preferable to use 1 mol-3 mol especially also from an industrial surface.

The solvent used in the step of reacting the compound represented by the above formula (I) and the compound represented by the above formula (II) is not particularly limited as long as the reaction proceeds, and methanol, ethanol, Alcohols such as isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol; esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate; Ethers such as diethyl ether, 1,4-dioxane, tetrahydrofuran and methylphenyl ether (anisole); Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone; Ethylene glycol monomethyl ether (methyl celloso) ), Glycol ethers (cellosolves) such as ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoethyl ether acetate (cellosolve acetate); dichloromethane, chloroform, carbon tetrachloride, 1, 2 -Halogenated aliphatic hydrocarbons such as dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene; alicyclic hydrocarbons such as cyclohexane Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; 1 halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene; Or it may be used two or more kinds. Among these, halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, and aromatic hydrocarbons such as benzene and toluene are preferable. 1 type (s) or 2 or more types can be used for a solvent.

In the step of reacting the compound represented by the above formula (I) with the compound represented by the above formula (II), a reaction accelerator may be used. Examples of the reaction accelerator include amine compounds such as ethyldiisopropylamine (DIPEA), pyridine, triethylamine, and DBU. These reaction accelerators may be used alone or in combination of two or more.

When using the said reaction accelerator, it is preferable that the usage-amount of a reaction accelerator is 1 mol-10 mol with respect to 1 mol of compounds represented by the said formula (I). More preferably, it is 1 mol-5 mol, Most preferably, it is 1 mol-3 mol.

The step of reacting the compound represented by the formula (I) with the compound represented by the formula (II) is preferably performed in an inert gas atmosphere. The inert gas is not particularly limited, and any of nitrogen, argon, helium and the like may be used, but nitrogen and argon are preferable. 1 type (s) or 2 or more types can be used for an inert gas.

The reaction temperature in the step of reacting the compound represented by the formula (I) with the compound represented by the formula (II) is preferably −78 ° C. to 100 ° C. More preferably, it is −30 ° C. to 80 ° C., and particularly preferably 0 ° C. to 50 ° C., although it depends on the solvent.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure.
The reaction time is preferably 10 minutes to 48 hours. More preferably, it is 30 minutes to 24 hours, and particularly preferably 1 hour to 12 hours from the viewpoint of industrial and practical use.

The boron-containing compound produced by the above-described method for producing a boron-containing compound of the present invention further comprises the following formula (III):

(Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or a monovalent substituent. M is the same or different and represents a metal element. N corresponds to the valence of the metal element. The compound represented by the above formula (I) and the compound represented by the above formula (II) by reacting the metal element-containing compound represented by R ¹ and / or R ² It is possible to replace the bromine atom or iodine atom bonded to the boron atom of the boron-containing compound obtained by the step of reacting with other substituents, thereby changing the substituent bonded to the boron atom in various ways. Boron-containing compounds can be produced.
Hereinafter, this reaction step is referred to as a dehalogenation step.

The dehalogenation step is represented by the boron-containing compound obtained by reacting the compound represented by the formula (I) with the compound represented by the formula (II), and the formula (III). As long as it includes a step of reacting the metal element-containing compound, other steps may be included. Further, a boron-containing compound obtained by reacting a compound represented by the above formula (I) with a compound represented by the above formula (II), and a metal element containing compound represented by the above formula (III) , One kind of compound may be used, or two or more kinds of compounds may be used.

In the dehalogenation step, the above formula (III) is used with respect to 1 mol of the boron-containing compound obtained by reacting the compound represented by the formula (I) with the compound represented by the formula (II). ) Is preferably used in an amount of 0.33 mol to 5 mol, although it depends on the valence of the metal element. More preferably, it is 0.67 mol-4 mol, Most preferably, it is 1 mol-3 mol also from an industrial and practical side.

Examples of the metal element M in the metal element-containing compound represented by the above formula (III) include aluminum, zinc, magnesium, lithium, copper and the like.
The R ¹ and ^{R 2,} represent the same as ^{R 1} and ^{R 2} of the boron-containing compound represented by the above formula (1).
When the metal element M is magnesium, it is preferable that at least one of R ¹ and R ² bonded to magnesium is a chlorine atom, a bromine atom, or an iodine atom. That is, the metal element-containing compound represented by the above formula (III) preferably contains MgCl, MgBr, or MgI in the structure.
When the metal element M is magnesium, a metal halide may be added during the reaction in the dehalogenation step. By adding a metal halide during the reaction in the dehalogenation step, the reaction yield in the dehalogenation step when the metal element-containing compound represented by the above formula (III) in which the metal element M is magnesium is used. The rate can be improved.

Examples of the halogen atom in the metal halide include a chlorine atom, a bromine atom, and an iodine atom, and examples of the metal element in the metal halide include zinc and aluminum. Among these, zinc chloride and zinc bromide are preferable as the metal halide.

Specific examples of the metal element-containing compound represented by the above formula (III) include lithium aluminum hydride, phenyl lithium, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diisopropyl zinc, diphenyl zinc, di (4-methoxy). Phenyl) zinc, bis (4-trifluoromethylphenyl) zinc, bis (pentafluorophenyl) zinc, trioctyl aluminum, phenyl magnesium bromide, 4-propylphenyl magnesium bromide, pentafluorophenyl magnesium bromide and the like. Among these, trioctyl aluminum, diphenyl zinc, and phenyl magnesium bromide are preferable.

The solvent used in the dehalogenation step is not particularly limited as long as the reaction proceeds, but the compound represented by the formula (I) is reacted with the compound represented by the formula (II). A solvent similar to the solvent used in the step can be used. Among these, toluene, dichloromethane, and diethyl ether are preferable. 1 type (s) or 2 or more types can be used for a solvent.

The dehalogenation step is preferably performed in an inert gas atmosphere. The inert gas is not particularly limited, and any of nitrogen, argon, helium and the like may be used, but nitrogen and argon are preferable. 1 type (s) or 2 or more types can be used for an inert gas.

The reaction temperature in the dehalogenation step is preferably −78 ° C. to 120 ° C. More preferably, it is −30 ° C. to 100 ° C., and particularly preferably 0 ° C. to 80 ° C., although it depends on the solvent. The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure. The reaction time is preferably 1 minute to 24 hours. More preferably, it is 3 minutes to 18 hours, and particularly preferably 5 minutes to 12 hours from the viewpoint of industrial and practical use.
In the method for producing a boron-containing compound represented by the formula (1) of the present invention, a step of reacting the compound represented by the above formula (I) with the compound represented by the above formula (II) is performed. Then, when performing the dehalogenation step, after purifying the boron-containing compound obtained by the step of reacting the compound represented by the formula (I) and the compound represented by the formula (II), The metal element-containing compound represented by the above formula (III) may be added and a dehalogenation step may be performed, and without purification, the compound represented by the above formula (I) and the above formula (II) After the step of reacting with the compound represented, the metal element-containing compound represented by the above formula (III) may be added to the dehalogenation step. Thus, the method for producing a boron-containing compound represented by the formula (1) of the present invention is also a useful method in that it can be selected whether or not a purification step is performed according to the purpose. be able to.

A boron-containing compound produced through the above-described dehalogenation step, or a boron-containing compound obtained by reacting the compound represented by the above formula (I) with the compound represented by the above (II) In the case of having a substituent having a reactive group such as the halogen atom described above as X ¹ and X ² in the formula (1), the ring structure is further reacted by a coupling reaction with an appropriate compound. Boron-containing compounds with various substituents bonded to can be produced. The coupling reaction is not particularly limited as long as it is a commonly used coupling reaction, and examples thereof include Suzuki coupling, Stille coupling, and Negishi coupling. As the reaction conditions for the coupling reaction, reaction conditions under which each coupling reaction is usually performed as described later can be appropriately employed.

In the boron-containing compound represented by the formula (1), at least one of X ¹ , X ² , R ¹ and R ^{2 in} the formula (1) is preferably a substituent having a reactive group.
The boron-containing compound represented by the above formula (1) has a combination of at least one reactive group capable of polycondensation in X ¹ , X ² , R ¹ and R ² , or X ¹ , X ² , R ¹ and R ² having a reactive group that can be polymerized alone can be suitably used as a raw material for the polymer. The boron-containing polymer obtained by polymerizing the monomer component containing the boron-containing compound in the present invention is also one aspect of the present invention. The boron-containing polymer of the present invention includes those having a repeating unit represented by the formula (7) described later and those having a repeating unit represented by the formula (11). Hereinafter, the boron-containing polymer having a repeating unit represented by the formula (7) and the boron-containing polymer having a repeating unit represented by the formula (11) are collectively referred to as the boron-containing polymer of the present invention. That's it.

A boron-containing polymer obtained by polymerizing a monomer component containing a boron-containing compound having a boron atom and a double bond, wherein the boron-containing compound has the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent, and the boron-containing compound is represented by the formulas X ¹ , X ² , A position in which at least one of R ¹ and R ² has a reactive group A boron-containing polymer characterized by being a substituent is also one aspect of the present invention.

The boron-containing polymer is a repeating unit formed by polycondensation of at least two groups of X ¹ , X ² , R ¹ and R ² in formula (1), or polymerization of at least one group. It is what has. That is, the following formula (7);

(In the formula, a dotted arc, a dotted line part in a skeleton part connecting a boron atom and a nitrogen atom, and an arrow from the nitrogen atom to the boron atom are the same as in the formula (1). X ¹ ′, X ² ′, R ¹ ′ and R ² ′ each represent the same group as X ¹ , X ² , R ¹ and R ² in formula (1), a divalent group, a trivalent group, or a direct bond. It is a boron containing polymer which has the structure of the repeating unit represented. The above formula (7) means that any one or more of X ¹ ′, X ² ′, R ¹ ′ and R ² ′ form a bond as part of the main chain of the polymer. When at least two groups of X ¹ , X ² , R ¹ and R ^{2 in} the formula (1) are polycondensed to form a boron-containing polymer, X ¹ ′ and X ² in the formula (7) are formed. At least two of ', R ¹ ' and R ² 'are a divalent group or a direct bond. When at least one group of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) is polymerized alone to form a boron-containing polymer, X ¹ ′, X in the above formula (7) ^At least one of ² ′, R ¹ ′ and R ² ′ is a trivalent group or a direct bond.
The boron-containing polymer having a repeating unit represented by the above formula (7) may be composed of one type of the structure represented by the above formula (7), and is represented by the above formula (7). Two or more structures may be included. When two or more types of structures represented by the above formula (7) are included, the two or more types of structures may be random polymers, block polymers, graft polymers, or the like. Further, when the polymer main chain is branched and there are three or more terminal portions, a dendrimer may be used.

Among the boron-containing polymer having a structural repeating unit represented by the above formula (7), the formula (7) R ^{1 'and} R ^2' in the, R ¹ and R ^2, respectively formula (1) Are preferably the same groups. Then, the equation (7) R ^{1 'and} R ^2' in it, linear or branched hydrocarbon group having 1 to 30 carbon atoms, it is an alicyclic hydrocarbon group having 3 to 30 carbon atoms Further preferred.
That is, a boron-containing polymer obtained by polymerizing a monomer component containing a boron-containing compound represented by the formula (1), wherein R ¹ and R ² in the formula (1) are the same or different, A linear or branched hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 30 carbon atoms is also one preferred embodiment of the present invention.

Of the specific examples of the structure of the repeating unit represented by the above formula (7), examples of the structure obtained by polycondensation include structures such as the following formulas (8-1) to (8-6). . Among these, the structures of (8-1) and (8-6) are preferable. More preferably, it is the structure of (8-1). That is, a boron-containing polymer obtained from a boron-containing compound having a structure represented by the formula (1), wherein X ¹ and X ² in the formula (1) are substituents having a reactive group, is also present. It is one of the inventions.

The combination of the reactive groups capable of polycondensation is not particularly limited as long as it can be polymerized. For example, carboxyl group and hydroxy group, carboxyl group and thiol group, carboxyl group and amino group, carboxylate ester and amino group. Group, carboxyl group and epoxy group, hydroxy group and epoxy group, thiol group and epoxy group, amino group and epoxy group, isocyanate group and hydroxy group, isocyanate group and thiol group, isocyanate group and amino group, hydroxy group and halogen atom, Thiol group and halogen atom, boryl group and halogen atom, stannyl group and halogen atom, aldehyde group and phosphonium methyl group, vinyl group and halogen atom, aldehyde group and phosphonate methyl group, haloalkyl group and haloalkyl group, sulfonium methyl group and sulfonium Butyl group, an aldehyde group and acetonitrile group, an aldehyde group and an aldehyde group, a halogen atom and a boryl group, a halogen atom and a magnesium halide, and a halogen atom and a halogen atom.
Among these, a combination of a halogen atom and a boryl group and a combination of a halogen atom and a halogen atom are preferable.

When at least two groups of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) are polycondensed to form a boron-containing polymer, X ¹ ′ and X ² in the above formula (7) At least two of ', R ¹ ' and R ² 'represent a divalent group or a direct bond, but the divalent group is not eliminated by a polycondensation reaction between substituents having a reactive group. It will represent a residue. When a substituent having a reactive group that forms a combination of reactive groups capable of polycondensation undergoes a polycondensation reaction, the residue may or may not remain in the polymer. In this case, at least one of X ¹ ′, X ² ′, R ¹ ′, and R ² ′ represents a residue that is not eliminated by a polycondensation reaction between substituents having a reactive group, in the latter case , At least one of X ¹ ′, X ² ′, R ¹ ′, and R ² ′ represents a direct bond.
Furthermore, when the repeating unit represented by formula (7) are two or more continues, between two repeating units, for ^example, -X 1 ^'-X 2'- as ^{in, X} 1', X ^{Two of 2} ′, R ¹ ′ and R ² ′ form a continuous bond. In this case, one of the two is a direct bond.

Specific examples of the case where a substituent having a reactive group that forms a combination of reactive groups capable of polycondensation causes a polycondensation reaction to leave a residue in the polymer include a substituent having a carboxyl group and a hydroxy group. The combination with the substituent which has group is mentioned. For example, when a —CH ₂ COOH group and a —CH ₂ CH ₂ OH group undergo a polycondensation reaction, the residue remaining in the polymer becomes a —CH ₂ (CO) —O—CH ₂ CH ₂ — group. Further, for example, when a substituent having a reactive group is composed only of a reactive group, such as a reaction between a —COOH group and an —OH group, the residue remaining in the polymer is — (CO) —O. -The basis.
Further, specific examples of the case where the combination of reactive groups capable of polycondensation causes a polycondensation reaction and no residue remains in the polymer include a combination of a boryl group and a halogen atom, or a combination of a halogen atom and a halogen atom. It is done.

Among specific examples of the structure of the repeating unit represented by the above formula (7), it is obtained by polymerizing at least one group of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) alone. As a structure, for example, a structure obtained by polymerizing X ² is a structure represented by the following formula (9). Thus, when X ² in formula (1) is a substituent having a reactive group that can be polymerized alone in the structure, X ² ′ is a trivalent group or a repeating unit having a structure in which it is a direct bond. It becomes. Similarly, when any of X ¹ , X ² , R ¹ or R ² in formula (1) is a substituent having a reactive group capable of being polymerized alone in the structure, X ¹ ′, X ² ′, R ¹ ′, and R ² ′ are a repeating unit having a structure in which a trivalent group or a direct bond is formed.

Examples of the reactive group that can be polymerized alone include 3,5-dibromophenyl group, alkenyl group, alkynyl group, epoxy group, and halogen atom. When the boron-containing compound of the above formula (1) has at least one of these groups, the boron-containing compound of the above formula (1) can be polymerized alone. Among these, an alkenyl group, an epoxy group, and a 3,5-dibromophenyl group are preferable.

Of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1), the polycondensable group may be a substituent having a reactive group capable of polycondensation in its structure. Similarly, the group that is homopolymerized may be any substituent that has a reactive group that can be polymerized alone in the structure. Examples of such a substituent include a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 7 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, and an aryl group. And a group in which a hydrogen atom of any group such as a heterocyclic group is substituted with a reactive group capable of polycondensation or a reactive group capable of being polymerized alone. Among these, a styryl group and a 3,5-dibromophenyl group are preferable.

As long as the boron-containing polymer of the present invention is obtained from the monomer component containing the boron-containing compound represented by the above formula (1), the monomer component contains other monomers. Also good.
That is, the boron-containing compound represented by the formula (1) and the following formula (10);

(In the formula, A represents a divalent group. X ³ and X ⁴ are the same or different and each represents a hydrogen atom or a monovalent substituent, and at least one group of X ³ and X ⁴ represents a reaction) The boron-containing polymer formed by polymerizing with other monomers represented by the above-mentioned substituents having a functional group is also included in the boron-containing polymer of the present invention.

A in the formula (10) is not particularly limited as long as it is a divalent group, and examples of the structure as a corresponding compound name include benzene, naphthalene, anthracene, phenanthrene, chrysene, rubrene, pyrene, perylene, Indene, azulene, adamantane, fluorene, fluorenone, dibenzofuran, carbazole, dibenzothiophene, furan, pyrrole, pyrroline, pyrrolidine, thiophene, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran , Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, trithiane, norbornene, benzofuran, indo , Benzothiophene, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzoxadiazole, purine, quinoline, isoquinoline, coumarin, sinoline, quinoxaline, acridine, phenanthroline, phenothiazine, flavone, triphenylamine, acetylacetone, dibenzoylmethane , Metal coordination compounds such as picolinic acid, silole, porphyrin, iridium, or derivatives having a substituent, polymers or oligomers containing the structures of these derivatives, and the like.
In addition, as said substituent, the thing similar to the substituent in said R < ¹ > and R < ² > can be used.

As said A, in addition to what was mentioned above, the structure of following formula (11-1)-(11-4) is mentioned, for example.

(In the formula, Ar 1, Ar 2 and Ar 3 are the same or different and each represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. Z 1 represents —C≡C—, —N ( Q3)-,-(SiQ4Q5) b- or a direct bond Z2 represents -CQ1 = CQ2-, -C≡C-, -N (Q3)-,-(SiQ4Q5) b- or directly Q1 and Q2 are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a hetero group Represents an aryloxycarbonyl group or a cyano group, Q3, Q4 and Q5 are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an aryl; .b .a represents an alkyl group represents an integer of 0 to 1 represents an integer of 1-12.)

The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the number of carbon atoms constituting the ring is usually about 6 to 60, preferably 6 to 20. The aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Examples of the arylene group include a phenylene group represented by the following formula (12-1), a naphthalenediyl group represented by the following formulas (12-2) to (12-3), and the following formula (12-4). To an anthracenediyl group represented by (12-7), a biphenyl-diyl group represented by the following formula (12-8), a fluorene-diyl group represented by the following formula (12-9), a formula (12 -10), a terphenyl-diyl group represented by the following formulas (12-11) to (12-12), and a stilbene-diyl group represented by the following formulas (12-13) to (12-14). Distylben-diyl groups, condensed ring compound groups represented by the following formulas (12-15) to (12-20), groups represented by the following formulas (12-21) to (12-23), and the like. It is done. Among these, a phenylene group, a biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferable.
In the formulas (12-1) to (12-23), R is the same or different and is a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, Arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, imido group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl Group or Roh represents a group. In the formula (12-1), a line attached so as to cross the ring structure like the line indicated by xy means that the ring structure is directly bonded to an atom in the bonded portion. That is, in the formula (12-1), it means that it is directly bonded to any of the carbon atoms constituting the ring indicated by the line xy, and the bonding position in the ring structure is not limited. Like the line indicated by z- in formula (12-10), a line attached to the apex of the ring structure means that the ring structure is directly bonded to an atom in the bonded portion at that position. . Moreover, the line with R attached so as to intersect the ring structure means that R may be bonded to the ring structure one or plural, and the bond The position is not limited.
In the formulas (12-1) to (12-10) and (12-15) to (12-20), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and a hydrogen atom May be substituted with a fluorine atom.

The said bivalent heterocyclic group means the remaining atomic groups remove | excluding two hydrogen atoms from the heterocyclic compound, and carbon number which comprises a ring is about 3-60 normally. As the heterocyclic compound, among organic compounds having a cyclic structure, the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic in the ring. Is also included.

Examples of the divalent heterocyclic group include a pyridine-diyl group represented by the following formula (13-1), a diazaphenylene group represented by the following formulas (13-2) to (13-3), Quinoline diyl groups represented by the following formulas (13-4) to (13-6), quinoxaline diyl groups represented by the following formulas (13-7) to (13-9), and the following formulas (13-10) to ( 13-12) includes acridinediyl group, bipyridyldiyl group represented by the following formula (13-13), and phenanthroline diyl group represented by the following formula (13-14) as a heteroatom. A divalent heterocyclic group;
Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as heteroatoms represented by the following formulas (13-15) to (13-17);
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom represented by the following formulas (13-18) to (13-20);
A 5-membered condensed heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom represented by the following formulas (13-21) to (13-26);
A 5-membered ring heterocyclic group represented by the following formulas (13-27) to (13-29) containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded at the α-position of the heteroatom. Groups that are in the form of bodies or oligomers;
A 5-membered heterocyclic group represented by the following formulas (13-30) to (13-35) containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to a phenyl group at the α-position of the heteroatom Group
Groups represented by the following formulas (13-36) to (13-38), wherein a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom is substituted with a phenyl group, a furyl group, or a thienyl group And the like.
In formulas (13-1) to (13-38), R is the same as R in the arylene group. Y represents O, S, SO, SO ₂ , Se, or Te. For the line attached to intersect the ring structure, the line attached to the apex of the ring structure, and the line with R attached to intersect the ring structure, the formulas (12-1) to (12-23) It is the same.
In formulas (13-1) to (13-38), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and the hydrogen atom may be replaced with a fluorine atom.

The divalent group having the metal complex structure is a remaining divalent group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand. The carbon number of the organic ligand is usually about 4 to 60. For example, 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof. Derivatives, 2-phenyl-benzoxazole and derivatives thereof, porphyrin and derivatives thereof, and the like.

Examples of the central metal of the metal complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium. The metal complex having the organic ligand includes a low-molecular fluorescent material, phosphorescence, and the like. Examples of the material include known metal complexes and triplet luminescent complexes.

Specific examples of the divalent group having the metal complex structure include groups represented by the following formulas (14-1) to (14-7).
In formulas (14-1) to (14-7), R is the same as R in the arylene group. About the line attached | subjected to the vertex of the ring structure, a direct coupling | bonding is meant like Formula (12-1)-(12-23).
In the formulas (14-1) to (14-7), the carbon atom may be replaced with a nitrogen atom, an oxygen atom or a sulfur atom, and the hydrogen atom may be replaced with a fluorine atom.

Moreover, as a structure of A, a structure like following formula (11-5) is also mentioned.

(In the formula, Ar 4, Ar 5, Ar 6 and Ar 7 are the same or different and represent an arylene group or a divalent heterocyclic group. Ar 8, Ar 9 and Ar 10 are the same or different and represent an aryl group or a monovalent heterocyclic ring. And o and p are the same or different and represent 0 or 1, and 0 ≦ o + p ≦ 1.

Specific examples of the structure represented by the above formula (11-5) include structures represented by the following formulas (15-1) to (15-8).

In the formulas (15-1) to (15-8), R is the same as R in the arylene group. About the line attached | subjected to the vertex of the ring structure, a direct coupling | bonding is meant like Formula (12-1)-(12-23). In the above formulas (15-1) to (15-8), one structural formula has a plurality of Rs, but they may be the same or different groups. In order to increase the solubility in a solvent, it is preferable to have one or more other than hydrogen atoms, and it is preferable that the symmetry of the shape of the structure including the substituent is small. Furthermore, in the above formulas (15-1) to (15-8), when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents. . Moreover, in the substituent in which R contains an alkyl chain, they may be linear, branched or cyclic, or a combination thereof. Examples of the non-linear group include, for example, isoamyl group, 2-ethylhexyl group 3,7-dimethyloctyl group, cyclohexyl group, 4-C1-C12 alkylcyclohexyl group and the like. In order to improve the solubility of the boron-containing copolymer of the present invention in a solvent, it is preferable that at least one alkyl chain having a cyclic or branched chain is contained.
A plurality of R may be connected to form a ring. Further, when R is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

Among the structures described above, the structure of A is preferably Formula (11-5), Formula (12-9), Formula (13-16), or Formula (13-28).

In the boron-containing polymer, at least one group of X ¹ , X ² , R ¹ and R ^{2 in} the formula (1) and at least one group of X ³ and X ^{4 in} the formula (10) are polymerized. It has a repeating unit formed. That is, the following formula (16);

(In the formula, a dotted arc, a dotted line part in a skeleton part connecting a boron atom and a nitrogen atom, and an arrow from the nitrogen atom to the boron atom are the same as in the formula (1). X ¹ ′, X ² ′, R ¹ 'and ^{R 2'} is the same as equation (7) .A are the same or different, .X ³ 'and ^{X 4'} represents a divalent group, ^{X 3} and respectively formula (10) A boron-containing polymer having a repeating unit structure represented by the same group as X ⁴ , a divalent group, a trivalent group, or a direct bond) is also included in the boron-containing polymer of the present invention. It is.
In the above formula (16), any one or more of X ¹ ′, X ² ′, R ¹ ′ and R ² ′, and any one or more of X ³ ′ and X ⁴ ′, It means forming a bond as part of the main chain of the polymer.
In the boron-containing polymer having a repeating unit represented by the above formula (16), the repeating unit derived from the above formula (1) and the repeating unit derived from the above formula (10) may be a random polymer, Either a polymer or a graft polymer may be used. Further, when the polymer main chain is branched and there are 3 or more terminal portions, it may be a dendrimer. The boron-containing polymer having a repeating unit represented by the above formula (16) is derived from the above formula (1). One type of repeating unit and one type of repeating unit derived from the above formula (10) may be included, or two or more types may be included. When two or more types of repeating units are included, the two or more types of structures may be a random polymer, a block polymer, or a graft polymer. Further, when the polymer main chain is branched and there are three or more terminal portions, a dendrimer may be used.

As the boron-containing polymer represented by the above formula (16), (i) any two of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) and the above formula (10) When X ³ and X ^{4 in the} above form a bond as part of the main chain of the polymer, (ii) any of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) Or one of X ³ and X ^{4 in} the above formula (10) may form a bond as part of the main chain of the polymer. As specific examples of the structure of the repeating unit in these cases, there are structures such as the following formulas (17) and (18), for example.

In the case of the structure of (i) above, specific examples of the structural portion derived from the above formula (1) among the repeating units represented by the above formula (16) include the above formulas (8-1) to (8-6). ). Among these, the structures of (8-1) and (8-6) are preferable. More preferably, it is the structure of (8-1).

Reaction when any group of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) is polycondensed with any group of X ³ and X ^{4 in} the above formula (10) Examples of the combination of the sex groups include the same ones as described above. That is, when any group of X ¹ , X ² , R ¹ and R ^{2 in} the above formula (1) and any group of X ³ and X ^{4 in} the above formula (10) are polycondensed Of the X ³ and X ^{4 in} the above formula (10), the polycondensation group is preferably any of the above-described substituents having a reactive group capable of polycondensation in its structure.
Further, when any of X ³ and X ^{4 in} the formula (10) is a substituent having a reactive group capable of being polymerized alone in the structure, the substituent can be polymerized alone as described above. It is preferably any of substituents having a reactive group in the structure.

The groups bonded to both ends of the boron-containing polymer of the present invention are not particularly limited, and may be the same or different. Examples of the group bonded to both ends include a hydrogen atom, a halogen atom, an aryl group optionally having a substituent, an oligoaryl group, a monovalent heterocyclic group, and a monovalent oligoheterocyclic group. Alkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, amino group, azo group, carboxyl group, acyl group, Examples include an alkoxycarbonyl group, a formyl group, a nitro group, a cyano group, a silyl group, a stannyl group, a boryl group, a phosphino group, a silyloxy group, an arylsulfonyloxy group, and an alkylsulfonyloxy group.

The boron-containing polymer of the present invention preferably has a weight average molecular weight of 10 ³ to 10 ⁸ . When the weight average molecular weight is in such a range, a thin film can be satisfactorily formed. More preferably, it is 10 < ³ > -10 < ⁷ >, More preferably, it is 10 < ⁴ > -10 < ⁶ >.
The weight average molecular weight can be measured by gel permeation chromatography (GPC apparatus, developing solvent: chloroform) in terms of polystyrene under the following apparatus and measurement conditions.
High-speed GPC device: HLC-8220GPC (manufactured by Tosoh Corporation)
Measurement condition:
Developing solvent Chloroform column TSK-gel GMHXL x 2 Eluent flow rate 1 ml / min
Column temperature 40 ° C

The boron-containing polymer of the present invention preferably has an LUMO energy level in the above-mentioned range, similarly to the boron-containing compound of the present invention. When the LUMO energy level of the boron-containing polymer is within such a range, it can be suitably used as a material for an organic EL device or an N-type semiconductor.

Further, like the boron-containing compound in the present invention, the boron-containing polymer also has a light emission quantum yield in the above-mentioned range, which is one of the preferred embodiments of the present invention. When the emission quantum yield of the boron-containing polymer is in such a range, sufficiently stable light emission can be obtained when used as a light-emitting material constituting a light-emitting layer in an organic EL device, a HOILED device, or the like. Therefore, it can be suitably used as a light-emitting material constituting a light-emitting layer, particularly as a light-emitting device used for an organic EL element, a HOILED element, or the like.

When manufacturing the boron containing polymer of this invention, the method of superposing | polymerizing the monomer component containing the boron containing compound represented by Formula (1) is mentioned. The monomer component may contain other monomers as long as it contains the boron-containing compound represented by the formula (1), but the formula (1) It is preferable that 0.1-99.9 mass% of boron containing compounds represented by this are included. More preferably, it is 10-90 mass%.
Further, in the polymerization reaction, the solid content concentration of the monomer component can be appropriately set within a range of 0.01% by mass to the maximum concentration at which it is dissolved. If the amount is too high, it may be difficult to control the reaction, so the content is preferably 0.1 to 20% by mass.

The other monomer preferably has a structure represented by the above formula (10). In addition, the said monomer component may contain 1 type of the boron containing compound represented by Formula (1), and the compound represented by Formula (10), and may contain 2 or more types.

In the compound represented by the above formula (10), X ³ and X ⁴ can be the same as the substituents having the reactive group in X ¹ and X ² described above.

When the boron-containing polymer of the present invention is formed by a polycondensation reaction, when the combination of the reactive groups is a combination of an aldehyde group and a phosphonium methyl group, a Wittig reaction causes a vinyl group and a halogen atom. In the case of a combination, by Heck reaction, in the case of a combination of aldehyde group and phosphonate methyl group, by Horner reaction, in the case of combination of haloalkyl group and haloalkyl group, by dehydrohalogenation method, sulfonium methyl In the case of a combination of a group and a sulfonium methyl group, the polymerization can be carried out by a sulfonium salt decomposition method. Further, when the combination of the reactive groups is a combination of an aldehyde group and an acetonitrile group, a halogen atom and a boryl group are obtained by a Knoevenagel reaction. In the case of a combination of the above, a Suzuki coupling reaction is performed. In the case of a combination of a halogen atom and a magnesium halide, a Grignard reaction is performed. In the case of a combination of a halogen atom and a halogen atom, a zero-valent nickel catalyst is formed. It can superpose | polymerize by the used Yamamoto polymerization reaction. In addition, examples of the polymerization method include a method of polymerizing with an oxidizing agent such as iron (III) chloride, a method of electrochemically oxidative polymerization, and the like.
Among these polymerization methods, the polymerization is preferably carried out by Suzuki coupling reaction or Yamamoto polymerization reaction.

The solvent used in the polymerization step is not particularly limited as long as the reaction proceeds. In the step of reacting the compound represented by the formula (I) with the compound represented by the formula (II). In addition to the solvent used, water, N, N-dimethylformamide, N-methylpyrrolidone, and dimethoxyethane can be used. Among these, toluene, tetrahydrofuran, and xylene are preferable. 1 type (s) or 2 or more types can be used for a solvent.
Among these, in the case of the Wittig reaction, Horner reaction, and Knoevenagel reaction, N, N-dimethylformamide, tetrahydrofuran, dioxane, and toluene are preferably used. In the case of the Heck reaction, a solvent having a relatively high boiling point, such as N, N-dimethylformamide, N-methylpyrrolidone, is preferably used. In the case of the Suzuki coupling reaction, N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran are preferably used. In the case of the above Grignard reaction, an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane or the like is preferably used, and a halide and metal magnesium are reacted in the solvent to form a Grignard reagent solution. A separately prepared solution containing a monomer component is mixed and a polymerization reaction is performed using a catalyst described later. In this case, it is preferable to add the catalyst while paying attention to excess reaction, and then carry out the reaction while raising the temperature and refluxing.
Moreover, when using the said solvent, in order to suppress a side reaction, it is preferable to fully deoxygenate so that reaction may advance in inert atmosphere. For the same reason, it may be preferable to perform a dehydration treatment. However, this is not the case when the reaction is carried out in a two-phase system with water, such as the Suzuki coupling reaction.

In the polymerization step, a catalyst may be used. In particular, the Heck reaction, Suzuki coupling reaction, a combination of reactive groups capable of polycondensation is a Stille polymerization reaction such as a stannyl group and a halogen atom, a Grignard reaction, When the polymerization is performed by the Yamamoto polymerization reaction, a catalyst is used.
Examples of catalysts for Heck reaction, Suzuki coupling reaction, and Stille polymerization include zero-valent palladium catalyst, divalent palladium salt catalyst, and the like. Specifically, tetrakistriphenylphosphine palladium, bis (tri-tert. -Butylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (tri-tert-butylphosphine) palladium, [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) chloride, tris (dibenzylideneacetone) ) Dipalladium (0), bis (tri-o-tolylphosphine) palladium, bis (1,2-bis (diphenylphosphino) ethane) palladium, bis (1,1 ′-(diphenylphosphino) ferrocene) palladium, Tet It can be exemplified tetrakis (triethyl phosphite) palladium, palladium (II) acetate, and the like. These catalysts may use 1 type and may use 2 or more types. Among these, tetrakistriphenylphosphine palladium and tris (dibenzylideneacetone) dipalladium (0) are preferable.
As the catalyst for performing the Grignard reaction, the above-mentioned zero-valent palladium catalyst, divalent palladium salt catalyst and nickel catalyst are preferably mentioned.
Moreover, when using the said catalyst, you may add ligands, such as a triphenylphosphine, a tricyclohexyl phosphine, and a trifuryl phosphine, as an additive.
In addition, as a method of mixing the catalyst with the reaction solution, the reaction solution is slowly added to the solution containing the catalyst while slowly adding the solution containing the catalyst while stirring the reaction solution in an inert atmosphere such as argon or nitrogen. And a method of adding them.

When using the said catalyst, it is preferable that it is 0.001-0.2 mol with respect to 1 mol of boron containing compounds represented by the said Formula (1) as the usage-amount of a catalyst. When the amount of the catalyst used is less than 0.001 mol, the function of the catalyst is not sufficiently exerted, and even when the amount is more than 0.2 mol, further improvement in the effect cannot be expected. Absent. More preferably, it is 0.005-0.15 mol, More preferably, it is 0.01-0.1 mol.

In the polymerization step, a polymerization initiator may be used. Polymerization initiators include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azo compounds such as azobis-2methylpropionamidine hydrochloride and azoisobutyronitrile; benzoyl peroxide, lauroyl Peroxides such as peroxide and cumene hydroperoxide can be used.
In addition, as a promoter, reducing agents such as sodium bisulfite, sodium sulfite, Mole salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid; and amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, glycine, etc. You can also.
These polymerization initiators and accelerators may be used alone or in combination of two or more.

When using the said polymerization initiator, it is preferable that it is 0.05 mass% or more as a usage-amount of a polymerization initiator with respect to 100 mass% of monomer components, and it is preferable that it is 5 mass% or less. The content is more preferably 0.1% by mass or more, and more preferably 1% by mass or less.
When using the said accelerator, it is preferable that it is 0.05 mass% or more, for example with respect to 100 mass% of monomer components, and it is preferable that it is 5 mass% or less. The content is more preferably 0.1% by mass or more, and more preferably 1% by mass or less.

In the polymerization, a chain transfer agent is preferably used for stable molecular weight control. One or more chain transfer agents may be used as necessary from the viewpoint of compatibility with monomers and solubility in a solvent. it can. As such a chain transfer agent, a thiol compound having a hydrocarbon group having 3 or more carbon atoms or a compound having a solubility in water at 25 ° C. of 10% or less is preferable. The chain transfer agent, butanethiol, octane described above Thiol, decanethiol, dodecanethiol, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, dodecyl mercaptan, mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercapto Thiol chain transfer agents such as propionic acid, 3-mercaptopropionic acid, thiomalic acid and 2-mercaptoethanesulfonic acid; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite) , Hya Etc. potassium) and sulfite are preferred.

The amount of the chain transfer agent used is preferably 0.1% by mass or more and preferably 10% by mass or less with respect to 100% by mass of the monomer component. The content is more preferably 0.5% by mass or more, and more preferably 5% by mass or less.

In the polymerization step, an alkali component may be added and the reaction may be performed in the presence of an alkali. In particular, in the case of the Wittig reaction, Heck reaction, Horner reaction, dehydrohalogenation method, Knoevenagel reaction, and Suzuki coupling reaction, the reaction is preferably performed in the presence of an alkali. Although it does not restrict | limit especially as said alkali component, For example, in Wittig reaction, Horner reaction, Knoevenagel reaction, metal alcoholates, such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate, lithium methylate; Hydride reagents such as sodium hydride; amides such as sodium amide can be used. In the case of the Heck reaction, triethylamine or the like can be used. In the case of the Suzuki coupling reaction, inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, and barium hydroxide; ammonium carbonates such as tetraethylammonium carbonate; organics such as triethylamine, trioctylmethylammonium chloride, and tetraethylammonium hydroxide Base: An inorganic salt such as cesium fluoride can be used. When the inorganic salt is used, the inorganic salt may be reacted in an aqueous solution in a two-phase system.
In addition, as a method of mixing the alkali component with the reaction solution, a method of slowly adding a solution containing an alkali component while stirring the reaction solution in an inert atmosphere such as argon or nitrogen, or reacting with a solution containing an alkali component. For example, a method of slowly adding the liquid.

The amount of the alkali component used is preferably equal to or greater than the functional group of the monomer component. In particular, in the case of Wittig reaction, Horner reaction, and Knoevenagel reaction, it is more preferably 1 to 3 equivalents, and in the case of Suzuki coupling reaction, it is more preferably 1 to 10 equivalents.

The polymerization step is preferably performed in an inert gas atmosphere. The inert gas is not particularly limited, and any of nitrogen, argon, helium and the like may be used, but nitrogen and argon are preferable. 1 type (s) or 2 or more types can be used for an inert gas.

The reaction temperature in the polymerization step is preferably 50 ° C to 200 ° C. In particular, in the case of the Wittig reaction, Horner reaction, and Knoevenagel reaction, the reaction can be allowed to proceed usually from about room temperature to about 150 ° C. In the case of the Heck reaction, the reaction can proceed at about 80 to 160 ° C. Moreover, in the case of a Suzuki coupling reaction, it can set according to a solvent, However, It is suitable to react at 50-160 degreeC.
The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but is preferably normal pressure.
The reaction time is preferably 5 hours or longer.
In particular, in the case of the Wittig reaction, Horner reaction, and Knoevenagel reaction, it is usually 5 minutes to 40 hours, preferably 10 minutes to 24 hours. In the case of the Heck reaction, it may be about 1 to 100 hours. In the case of the Suzuki coupling reaction, it may be about 1 to 200 hours.
The polymerization reaction can be carried out either batchwise or continuously.

In the case of the Grignard reaction, the amount of the Grignard reagent used is preferably equal to or greater than the monomer component. More preferably, it is 1-1.5 equivalent, More preferably, it is 1-1.2 equivalent.

The boron-containing compound of the present invention and the boron-containing polymer of the present invention can be suitably used as materials for organic EL devices and N-type semiconductors. Organic EL elements include those having a structure in which an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially laminated, or those having a hole injection layer and an electron injection layer. In these devices, electrons injected from the cathode pass through the electron transport layer and reach the light emitting layer. From the viewpoint of energy efficiency, the minimum empty orbit (LUMO) of the material of the light emitting layer and the electron transport layer is used. ) Preferably has a small energy gap between the LUMO energy level of the electron injection layer material and the valence band of the cathode. As the cathode, metals such as aluminum, magnesium, calcium, and alloys thereof are used. Of these, those having a high valence band energy are easily oxidized, so use a low energy one. Is preferred. By using a boron-containing compound with a low energy level of the lowest unoccupied orbital (LUMO), it is possible to use a material with a low valence band energy and a low oxidation potential as the cathode, so the cathode can be freely selected. Can expand the degree.
Therefore, from such a point, the boron-containing compound in the present invention and / or the boron-containing polymer in the present invention can be suitably used as a material for an organic EL device or an N-type semiconductor. Thus, it is also one aspect of the present invention that the light-emitting material of the present invention and / or the boron-containing polymer of the present invention containing the boron-containing compound represented by the above formula (1) is used for forming a light-emitting device. is there. Such a light-emitting device formed using the light-emitting material of the present invention containing the boron-containing compound represented by the above formula (1) or the boron-containing polymer of the present invention is also one aspect of the present invention.
Furthermore, among the boron-containing compound in the present invention and the boron-containing polymer of the present invention, those having an emission quantum yield of 20 to 100% can obtain stable light emission from the high emission quantum yield. Therefore, it is preferable to be used for forming a light emitting layer of an organic EL element or a HOILED element among light emitting devices.

The boron-containing compound in the present invention has the above-described configuration, has a low LUMO energy level, and has a high emission quantum yield. Therefore, the boron-containing compound is suitable as a light-emitting material for organic EL elements, N-type semiconductors, and HOILED elements. It can be used.

It is a reaction formula showing reaction of Example 1-1. It is a reaction formula showing reaction of Example 2-1. It is a reaction formula showing reaction of Example 2-34. 4 is a reaction formula showing the reaction of Example 3.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following examples and comparative examples, various physical properties were measured as follows.
^<1 H-NMR>
The obtained boron-containing compound was measured as a deuterated chloroform solution using a high-resolution nuclear magnetic resonance apparatus (product name “Gemini 2000”; 300 MHz, manufactured by Varian, Inc.). The chemical shift was recorded as 1 / 1,000,000 (ppm; δ scale) on the low magnetic field side from tetramethylsilane, and the hydrogen nucleus (δ0.00) of tetramethylsilane was referred to.
< ^13C -NMR>
The obtained boron-containing compound was measured as a deuterated chloroform solution using a high-resolution nuclear magnetic resonance apparatus (product name “Gemini 2000”; 75 MHz, manufactured by Varian, Inc.). Chemical shifts are recorded from tetramethylsilane as parts per million (ppm; δ scale) on the low magnetic field side, and carbon nuclei (CDCl ₃ : δ = 77.0, CD ₂ Cl ₂ : δ = 53 in the NMR solvent). .1, CD ₃ CN: δ = 1.32, DMSO-d ₆ : δ = 39.52).
^<11 B-NMR>
The obtained boron-containing compound was measured as a deuterated chloroform solution using a high-resolution nuclear magnetic resonance apparatus (product name “Mercury-400”; 128 MHz, manufactured by Varian, Inc.). Chemical shifts were recorded as parts per million (ppm; δ scale) based on the boron nucleus (δ = 0.00) of the boron trifluoride-diethyl ether complex.
<High resolution mass spectrometry spectrum>
Using a high-resolution mass spectrometer (product names “JMS-SX101A”, “JMS-MS700”, “JMS-BU250”, manufactured by JEOL Ltd.), electron ionization (EI) or fast electron impact (FAB) It was measured.

<Weight average molecular weight>
The weight average molecular weight was measured by gel permeation chromatography (GPC apparatus, developing solvent: chloroform) in terms of polystyrene under the following apparatus and measurement conditions.
High-speed GPC device: HLC-8220GPC (manufactured by Tosoh Corporation)
Measurement condition:
Developing solvent Chloroform column TSK-gel GMHXL x 2 Eluent flow rate 1 ml / min
Column temperature 40 ° C

<LUMO energy levels>
A p-doped silicon substrate (manufactured by Furuuchi Chemical Co., Ltd.) was cut into 25 mm squares, ultrasonically cleaned in acetone and isopropyl alcohol for 10 minutes, respectively, and then subjected to UV ozone treatment for 20 minutes. When the sample was a low molecular compound, this substrate was fixed to a substrate holder of a vacuum deposition apparatus (manufactured by ULVAC) connected to a glove box in an argon atmosphere. A sample to be measured was put in a quartz crucible, decompressed to about 1 × 10 ⁻³ Pa, and evaporated to a thickness of 10 nm to obtain a measurement sample. When the sample was a polymer compound, a sample solution adjusted to a concentration of 0.5 to 2% by weight was dropped on this substrate and spin-coated at a speed of 1000 to 3000 revolutions per minute to obtain a measurement sample. About the created measurement sample, the ionization potential was measured using the ultraviolet photoelectron spectrometer (made by Kobelco Research Institute). The measured value was defined as the energy level of the highest occupied orbit (HOMO) of the sample.
At the same time, an absorption spectrum of another sample thin film prepared in the same manner as described above was measured using an ultraviolet-visible spectrophotometer (product name “Agilent 8453”, manufactured by Agilent Technologies). From the obtained spectrum, the long wavelength side absorption edge λ (unit: nm) of the absorption peak was read, and the HOMO-LUMO gap (BG) was determined by the following mathematical formula (1).

Furthermore, from the HOMO energy level obtained using the composite electron spectrometer as described above and the HOMO-LUMO gap (BG) obtained from the above equation (1), the following equation (2) is obtained. The energy level of LUMO was obtained.

<Fluorescence spectrum>
A dilute dichloromethane solution of a boron-containing compound was prepared, and a fluorescence spectrum was measured using a fluorescence spectrophotometer (product name “FP-777”, manufactured by JASCO Corporation) under the following measurement conditions.
Measurement conditions Measurement temperature: Wavelength of room temperature excitation light: 320 nm or 370 nm (however, an appropriate wavelength is selected according to the absorption peak position of the absorption spectrum of the sample)
Measurement wavelength range: 330 to 600 nm
<Luminescent quantum yield>
For the boron-containing compound, several types of dichloromethane solutions having different concentrations were prepared, and the absorbance of each solution was measured using an ultraviolet-visible spectrophotometer (product name “Agilent 8453”, manufactured by Agilent Technologies). Moreover, the fluorescence spectrum of each solution was measured and the fluorescence intensity (wave number integral value) was determined. From the obtained absorbance and fluorescence intensity, a graph was prepared with the horizontal axis representing the absorbance and the vertical axis representing the fluorescence intensity. Further, as a standard substance, a 0.1M sulfuric acid solution of quinine sulfate was similarly measured, and each graph was similarly prepared. Inclination G _S graphs for boron-containing compound (a straight line with a positive _{correlation),} the slope of the graph for quinine sulfate G _R, the n _S refractive index of _{dichloromethane,} the refractive index of 0.1M sulfuric acid The emission quantum yield Y _S of the boron-containing compound was determined by the following mathematical formula (3), where n _R and quinine sulfate (document values) were Y _{R. Incidentally,} n _S, n R, the _{Y R} as literature _{values, n S = 1.4242, n R} = 1.333, using each value of Y R = 0.54.

(Example 1-1)
Under an argon atmosphere, 0.5 ml of dichloromethane was added to boron triiodide (215.34 mg, 0.5 mmol), cooled to 0 ° C., 2-phenylpyridine (77.6 mg, 0.5 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Stir. After cooling to 0 ° C., it was quenched with water, extracted with chloroform, the organic layer was washed with a saturated aqueous sodium chloride solution, and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting solid was washed with hexane to obtain 160 mg of boron complex 1 in a yield of 48%.
The reaction formula of this reaction is shown in FIG.

(Example 1-2)
A reaction was carried out in the same manner as in Example 1-1 except that the boron triiodide in Example 1-1 was changed to boron tribromide, and boron complex 2 was obtained in a yield of 73%.

(Reference Examples 1-1 to 1-4)
The reaction was carried out in the same manner as in Example 1-1 except that the boron triiodide in Example 1-1 was changed to the Lewis acid shown in Table 1. Reaction conditions and reaction results are shown in Table 1. In Table 1, “no reaction” indicates that the reaction did not proceed.

(Example 1-3)
Under an argon atmosphere, ethyldiisopropylamine (65 mg, 0.50 mmol) was added to a dichloromethane solution (0.5 ml) containing 2-phenylpyridine (78 mg, 0.50 mmol), and then boron tribromide (1 0.0M, 1.5 ml, 1.5 mmol) was added and stirred at room temperature for 9 hours. The reaction solution was cooled to 0 ° C., saturated aqueous potassium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (19);

A boron complex 3 represented by the formula (145 mg, 0.45 mmol) was obtained in a yield of 89%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.42 (t, J = 7.5 Hz, 1H), 7.55-7.60 (m, 2H), 7.75 (d, J = 7.8 Hz, 1H) ), 7.87 (d, J = 7.5 Hz, 1H), 7.93 (d, J = 7.8 Hz, 1H), 8.16 (t, J = 7.8 Hz, 1H), 8.95. (D, J = 5.4 Hz, 1H); ¹¹ B-NMR (CDCl ₃ ): δ-1.1;

(Example 1-4)
In an argon atmosphere, ethyldiisopropylamine (65 mg, 0.50 mmol) was added to a dichloromethane solution (0.5 ml) containing 2- (4-methylphenyl) pyridine (85 mg, 0.50 mmol), and then at 0 ° C. Boron bromide (1.0 M, 1.5 ml, 1.5 mmol) was added and stirred at room temperature for 9 hours. The reaction solution was cooled to 0 ° C., saturated aqueous potassium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (20);

The boron complex 4 represented by (150 mg, 0.44 mmol) was obtained with a yield of 89%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 2.47 (s, 3H), 7.20-7.27 (m, 1H), 7.48-7.53 (m, 1H), 7.63 (d, J = 8.1 Hz, 1H), 7.68 (s, 1H), 7.84-7.87 (m, 1H), 8.09-8.15 (m, 1H), 8.90 (d, ¹³ C-NMR (CDCl ₃ ): δ22.1, 118.1, 121.9, 123.1, 129.7, 130.8, 131.2, 143.6, J = 6.0 Hz, 1H); 144.0, 144.1, 156.0; ¹¹ B-NMR (CDCl ₃ ): δ-1.1;

(Example 1-5)
After adding ethyldiisopropylamine (39 mg, 0.30 mmol) to a dichloromethane solution (0.3 ml) containing 5-bromo-2- (4-bromophenyl) pyridine (94 mg, 0.30 mmol) under an argon atmosphere, Boron tribromide (1.0 M, 0.9 ml, 0.9 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 9 hours. The reaction solution was cooled to 0 ° C., saturated aqueous potassium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (21);

The boron complex 5 represented by (40 mg, 0.082 mmol) was obtained in a yield of 28%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): 7.57-7.59 (m, 2H), 7.80 (dd, J = 8.4, 0.6 Hz, 1H), 7.99 (s, 1H), 8.27 (dd, J = 8.4, 2.1 Hz, 1H), 9.01 (d, J = 1.5 Hz, 1H);

(Example 1-6)
Ethyldiisopropylamine (39 mg, 0.30 mmol) was added to a dichloromethane solution (0.3 ml) containing 2-phenylquinoline (62 mg, 0.30 mmol) under an argon atmosphere, and then boron tribromide (1 0.0 M, 0.9 ml, 0.9 mmol) was added, and the mixture was stirred at room temperature for 9 hours. The reaction solution was cooled to 0 ° C., saturated aqueous potassium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (22);

The boron complex 6 represented by (85 mg, 0.23 mmol) was obtained with a yield of 75%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.44 (td, J = 7.5, 1.0 Hz, 1H), 7.65 (td, J = 7.5, 0.9 Hz, 1H), 7.73 (Ddd, J = 8.1, 7.2, 1.1 Hz, 1H), 7.87 (d, J = 7.5 Hz, 1H), 7.96-8.09 (m, 4H), 8. 60 (d, J = 9.0 Hz, 1H), 9.29 (d, J = 8.7 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ 115.1, 122.6, 124.5, 128 , 118.5, 128.6, 128.9, 130.5, 132.9, 133.4, 133.8, 140.6, 145.0, 157.6; ¹¹ B-NMR (CDCl ₃ ): Δ-1.8;

(Example 1-7)
Under an argon atmosphere, boron tribromide (1.0 M, 2.0 ml, 2.0 mmol) was added at 0 ° C. to a dichloromethane solution (0.5 ml) containing 2-phenylpyrimidine (78 mg, 0.50 mmol) at room temperature. For 1 hour. The reaction solution was cooled to 0 ° C., a saturated aqueous sodium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (23);

The boron complex 7 represented by the formula (148 mg, 0.45 mmol) was obtained in a yield of 91%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.49 (td, J = 7.6, 1.1 Hz, 1H), 7.56 (dd, J = 5.7, 4.8 Hz, 1H), 7.67 (Td, J = 7.4, 1.1 Hz, 1H), 7.89 (d, J = 7.5 Hz, 1H), 8.10 (dt, J = 7.5, 0.9 Hz, 1H), 9.10-9.14 (m, 2H); ¹³ C-NMR (CDCl ₃ ): δ 119.1, 124.3, 129.1, 130.3, 132.4, 134.9, 151.2, ¹¹ B-NMR (CDCl ₃ ): δ-2.4; HRMS (FAB) C ₁₀ H ₇ BBr ₂ N ₂ (M ⁺ ): Theoretical value 323.9069, measured value 323. 9073

(Example 1-8)
Under argon atmosphere, boron tribromide (1.0 M, 0.60 ml, 0.60 mmol) was added to a dichloromethane solution (0.5 ml) containing 2- (2-pyridyl) benzothiophene (105 mg, 0.50 mmol) at 0 ° C. ) And stirred at room temperature for 1 hour. The reaction solution was cooled to 0 ° C., a saturated aqueous sodium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (24);

The boron complex 8 represented by (93 mg, 0.24 mmol) was obtained with a yield of 49%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.41-7.52 (m, 3H), 7.59 (d, J = 8.1 Hz, 1H), 7.89 (dd, J = 7.4, 1 .4 Hz, 1H), 8.09 (td, J = 7.8, 1.5 Hz, 1H), 8.20-8.22 (m, 1H), 8.90 (d, J = 5.7 Hz, ¹¹ B-NMR (CDCl ₃ ): δ-3.9; HRMS (FAB) C ₁₃ H ₈ BBr ₂ NS (M ⁺ ): Theoretical value 378.8837, Actual value 378.8838

(Example 1-9)
Boron tribromide in a dichloromethane solution (0.5 ml) containing 1,4-di (2-pyridinyl) benzene (116 mg, 0.50 mmol) at 0 ° C. in an argon atmosphere at 0 ° C. (1.0 M, 3.0 ml, 3.0 mmol) was added and stirred at room temperature for 48 hours. The reaction solution was cooled to 0 ° C., saturated aqueous potassium carbonate solution was added, and the mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with water and chloroform to obtain the following formula (25);

The boron complex 9 represented by the formula (210 mg, 0.37 mmol) was obtained in a yield of 73%.

(Example 2-1)
Under an argon atmosphere, trimethylaluminum (1.1 M, 0.20 ml, 0.22 mmol) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol), Stir at room temperature for 5 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 2: 1) to obtain the following formula (26);

Boron complex 10 (18 mg, 0.091 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 91%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.05 (s, 6H), 7.26-7.38 (m, 2H), 7.43 (td, J = 7.5, 0.9 Hz, 1H), 7.65 (d, J = 7.2 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.93-7.99 (m, 2H), 8.44 (dt, J = 5.7, 1.2 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ8.8, 117.7, 121.3, 121.5, 125.1, 129.1, 130.2, 135 , 139.2, 142.1, 156.8; ¹¹ B-NMR (CDCl ₃ ): δ1.1; HRMS (EI) C ₁₃ H ₁₃ BN ([M−H] ⁺ ): Theoretical value 194. 1141, actually measured value 194.1136
The reaction formula of this reaction is shown in FIG.

(Examples 2-2 to 2-9)
As shown in Table 2, the reaction was performed in the same manner as in Example 2-1 except that the organometallic reagent, the solvent, and the reaction conditions were changed, and boron complexes 11 to 18 were obtained. Reaction conditions and reaction results are shown in Table 2.
In Table 2, the amount of organometallic reagent used represents the number of moles when the amount of 2- (2-dibromoborylphenyl) pyridine used as a substrate is 1 mole. “Full conversion” indicates that the reaction itself is completely completed. “Sm.remained” indicates that the raw material substrate remains. “Complex mixture” indicates that the target product is generated, but is a complex mixed system that cannot be purified.

(Example 2-10)
Under an argon atmosphere, lithium aluminum hydride (8.0 mg, 0.21 mmol) was added to a diethyl ether solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol), and at room temperature. Stir for 1 hour. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (27);

The boron complex 19 represented by (13 mg, 0.080 mmol) was obtained with a yield of 80%. The luminescence quantum yield in the solution was 35%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 2.8-4.0 (br, 2H), 7.30-7.35 (m, 2H), 7.46 (t, J = 7.4 Hz, 1H), 7.80 (d, J = 7.2 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.93-8.00 (m, 2H), 8.64 (d, J = 5.7 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ 117.9, 120.7, 121.5, 125.2, 130.1, 130.2, 136.6, 139.1, 143 , 158.4; ¹¹ B-NMR (CDCl ₃ ): δ-8.1; HRMS (EI) C ₁₀ H ₉ BN ([M−H] ⁺ ): Theoretical value 166.0828, measured value 166. 0827

(Example 2-11)
Triethylaluminum (0.94M, 0.22 ml, 0.20 mmol) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol) under an argon atmosphere, Stir at room temperature for 5 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 3: 2) to obtain the following formula (28);

Boron complex 20 (18 mg, 0.082 mmol) represented by the formula (wherein Et represents an ethyl group) was obtained in a yield of 82%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.41-0.61 (m, 8H), 0.69-0.85 (m, 2H), 7.27-7.37 (m, 2H), 7. 42 (td, J = 7.3, 0.7 Hz, 1H), 7.65 (d, J = 7.2 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.93. −7.99 (m, 2H), 8.36 (dt, J = 6.0, 1.2 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ9.9, 16.7, 117.5, 121.1, 121.2, 125.0, 129.6, 129.8, 136.1, 139.0, 141.9, 157.7; ¹¹ B-NMR (CDCl ₃ ): δ3.6; HRMS _{(EI) C 15 H 17 BN} ([M-H] +): theory 222.1454, found 222 1450

(Example 2-12)
Under an argon atmosphere, diisopropyl zinc (1.0 M, 0.11 ml, 0.11 mmol) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol), The mixture was stirred at 70 ° C. for 12 hours. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (29);

Boron complex 21 (19 mg, 0.077 mmol) represented by (wherein ⁱ Pr represents an isopropyl group) was obtained in a yield of 77%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.51 (d, J = 7.5 Hz, 6H), 0.62 (d, J = 7.2 Hz, 6H), 1.18 (sept, J = 7.2 Hz) , 2H), 7.25-7.41 (m, 3H), 7.63 (dt, J = 7.2, 0.9 Hz, 1H), 7.82 (dt, J = 7.8, 0.8). 9 Hz, 1H), 7.94-8.00 (m, 2H), 8.36 (dt, J = 5.7, 1.6 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ 19.3. 19.8, 117.4, 120.7, 121.0, 124.9, 129.7, 129.9, 136.6, 138.9, 142.3, 158.0; ¹¹ B-NMR (CDCl ₃ ): δ 4.6; HRMS (FAB) C ₁₇ H ₂₃ BN ([M + H] ⁺ ): Theory Value 252.1924, measured value 252.1933

(Example 2-13)
Under an argon atmosphere, diphenylzinc (0.28M, 0.75 ml, 0.21 mmol) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol), Stir at room temperature for 12 hours. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (30);

Boron complex 22 (31 mg, 0.098 mmol) represented by (wherein Ph represents a phenyl group) was obtained in a yield of 98%. Moreover, the light emission quantum yield in the solution was 28%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.14-7.24 (m, 10H), 7.31-7.38 (m, 2H), 7.44 (t, J = 7.4 Hz, 1H), 7.74 (d, J = 6.9 Hz, 1H), 7.87 (d, J = 7.5 Hz, 1H), 8.02-8.04 (m, 2H), 8.51 (d, J = 5.7 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ 118.1, 121.6, 121.8, 125.6, 125.9, 127.4, 130.7, 131.2, 133 , 135.8, 140.4, 144.0, 158.3; ¹¹ B-NMR (CDCl ₃ ): δ3.4; HRMS (EI) C ₂₃ H ₁₈ BN (M ⁺ ): Theoretical value 319. 1532, measured value 319.1532

(Example 2-14)
Under an argon atmosphere, di (4-methoxyphenyl) zinc (0.13M, 1.6 ml, 0 ml) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol). .21 mmol) was added and stirred at 70 ° C. for 12 hours. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 2) to obtain the following formula (31);

Boron complex 23 (34 mg, 0.090 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 90%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 3.76 (s, 6H), 6.76-6.80 (m, 4H), 7.13-7.17 (m, 4H), 7.30-7. 36 (m, 2H), 7.44 (td, J = 7.2, 0.9 Hz, 1H), 7.71 (d, J = 7.5 Hz, 1H), 7.87 (d, J = 7 .5 Hz, 1H), 8.00-8.02 (m, 2H), 8.47-8.50 (m, 1H); ¹³ C-NMR (CDCl ₃ ): δ 54.9, 113.0, 118 0.0, 121.6, 121.8, 125.8, 130.7, 131.2, 134.1, 135.7, 140.3, 144.0, 157.9, 158.2; ¹¹ B- _{NMR (CDCl 3): δ3.8;} HRMS (EI) C 25 H 22 BNO 2 (M +): theory 379.1744, found 379.1734

(Example 2-15)
Under an argon atmosphere, bis (4-trifluoromethylphenyl) zinc (0.26M, 0.80 ml) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyridine (32 mg, 0.10 mmol). 0.21 mmol) and stirred at room temperature for 30 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (32);

The boron complex 24 represented by the formula (41 mg, 0.090 mmol) was obtained with a yield of 90%. The luminescence quantum yield in the solution was 36%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.29 (m, 4H), 7.36-7.50 (m, 7H), 7.68 (d, J = 6.6 Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 8.08-8.16 (m, 2H), 8.43 (d, J = 6.0 Hz, 1H); ¹¹ B-NMR (CDCl ₃ ): Δ2.7; HRMS (EI) C ₂₅ H ₁₆ BF ₆ N ([M−H] ⁺ ): Theoretical value 454.1202, measured value 454.1205

(Example 2-16)
Under an argon atmosphere, bis (pentafluorophenyl) zinc (88 mg, 0.22 mmol) was added to a toluene solution (1.5 ml) containing 2- (2-dibromoborylphenyl) pyridine (65 mg, 0.20 mmol), and 70 Stir at 15 ° C. for 15 hours. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (33);

A boron complex 25 represented by the formula (89 mg, 0.089 mmol) was obtained in a yield of 89%. The luminescence quantum yield in the solution was 58%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.37-7.49 (m, 3H), 7.76 (d, J = 7.5 Hz, 1H), 7.87 (d, J = 7.5 Hz, 1H ), 8.05 (d, J = 8.1 Hz, 1H), 8.15 (td, J = 7.7, 1.3 Hz, 1H), 8.59 (d, J = 5.7 Hz, 1H) ¹³ C-NMR (CDCl ₃ ): δ 118.5, 121.8, 122.4, 127.2, 130.3, 132.0, 135.1, 135.2-149.5 (m), 142 ¹¹ B-NMR (CDCl ₃ ): δ-2.3; HRMS (EI) C ₂₃ H ₈ BF ₁₀ N (M ⁺ ): Theoretical value 499.590, measured value 499.0583

(Example 2-17)
Under an argon atmosphere, trimethylaluminum (1.4 M, 0.59 ml, 0.82 mmol) was added to a toluene solution (4.0 ml) containing 2- (2-dibromoboryl-4-methylphenyl) pyridine (136 mg, 0.40 mmol). And stirred at room temperature for 10 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and then purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (34);

Boron complex 26 (83 mg, 0.40 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 99%. The luminescence quantum yield in the solution was 49%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.04 (s, 6H), 2.45 (s, 3H), 7.10-7.12 (m, 1H), 7.28-7.33 (m, 1H), 7.46 (s, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.87-7.95 (m, 2H), 8.40 (d, J = 5. ¹³ C-NMR (CDCl ₃ ): δ 9.0, 22.1, 117.4, 120.8, 121.4, 126.3, 129.8, 132.7, 139.1, 7Hz, 1H); 140.5, 142.1, 157.0; ¹¹ B-NMR (CDCl ₃ ): δ1.0; HRMS (EI) C ₁₄ H ₁₅ BN ([M−H] ⁺ ): Theoretical value 208.1298, measured. Value 208.1290

(Example 2-18)
In a mixed solvent of a toluene solution (1.0 ml) containing 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (170 mg, 0.35 mmol) and dichloromethane (1.0 ml) under an argon atmosphere, Trimethylaluminum (1.4M, 0.53 ml, 0.74 mmol) was added and stirred at room temperature for 1 hour. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (35);

Boron complex 27 (112 mg, 0.32 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 91%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.03 (s, 6H), 7.41 (dd, J = 8.1, 1.5 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H) ), 7.73 (d, J = 2.1 Hz, 1H), 7.80 (d, J = 8.4 Hz, 1H), 8.08 (dd, J = 8.7, 2.1 Hz, 1H) , 8.49 (d, J = 2.1 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ8.7, 116.9, 118.7, 123.0, 126.7, 128.6, 132 , 132.9, 142.4, 143.8, 154.9; ¹¹ B-NMR (CDCl ₃ ): δ1.9; HRMS (EI) C ₁₃ H ₁₁ BBr ₂ N ([M−H] ⁺ ): Theoretical value 3499.9351, measured value 3499.9334

(Example 2-19)
Under a mixed atmosphere of a toluene solution (5.0 ml) containing 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (400 mg, 0.83 mmol) and dichloromethane (5.0 ml) under an argon atmosphere, Trioctylaluminum (1.4M, 3.6 ml, 1.7 mmol) was added and stirred at room temperature for 10 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by preparative thin layer chromatography (hexane: ethyl acetate = 10: 1) to obtain the following formula (36);

Boron complex 28 (400 mg, 0.73 mmol) represented by the formula ( ^{where n} Oct represents an octyl group) was obtained in a yield of 88%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.45-1.24 (m, 34H), 7.41 (dd, J = 8.4, 1.8 Hz, 1H), 7.65 (d, J = 8 .1 Hz, 1H), 7.73 (d, J = 1.8 Hz, 1H), 7.80 (d, J = 8.7 Hz, 1H), 8.07 (dd, J = 8.7, 1 Hz, 1H), 8.43 (d, J = 1.8 Hz, 1H); ¹³ C-NMR (CDCl ₃ ): δ14.2, 22.7, 25.3, 26.2, 29.4, 29 .6, 31.9, 33.6, 116.7, 118.5, 122.9, 126.4, 128.4, 132.6, 133.7, 142.1, 143.4, 155.5 _{^{; 11 B-NMR (CDCl 3}} ): δ3.8; HRMS (FAB) C 27 H 41 BBr 2 N [M ^{+ H] +):} theory 548.1699, found 548.1694

(Example 2-20)
Under an argon atmosphere, trimethylaluminum (1.4 M, 0.48 ml, 0.67 mmol) was added to a toluene solution (2.0 ml) containing 2- (2-dibromoborylphenyl) quinoline (120 mg, 0.32 mmol), Stir at room temperature for 5 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (37);

Boron complex 29 (64 mg, 0.26 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 82%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.32 (s, 6H), 7.35 (td, J = 7.2, 0.9 Hz, 1H), 7.51 (td, J = 7.2, 0 .9 Hz, 1H), 7.61 (t, J = 7.4 Hz, 1H), 7.74 (dd, J = 7.2, 0.9 Hz, 1H), 7.86 (ddd, J = 8. 4, 6.9, 1.5 Hz, 1H), 7.92-7.98 (m, 2H), 8.06 (d, J = 8.7 Hz, 1H), 8.38 (d, J = 8 .7 Hz, 1 H), 8.66 (d, J = 9.0 Hz, 1 H); ¹³ C-NMR (CDCl ₃ ): δ 9.3, 115.6, 122.3, 123.4, 125.2 126.3, 127.6, 128.7, 128.8, 130.8, 131.3, 135.3, 140.3, 142. ¹¹ B-NMR (CDCl ₃ ): δ2.5; HRMS (EI) C ₁₇ H ₁₅ BN ([M−H] ⁺ ): Theoretical value 244.1298, measured value 244.1289

(Example 2-21)
Under an argon atmosphere, trimethylaluminum (1.1 M, 0.20 ml, 0.21 mmol) was added to a toluene solution (1.0 ml) containing 2- (2-dibromoborylphenyl) pyrimidine (33 mg, 0.10 mmol), Stir at room temperature for 10 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (38);

Boron complex 30 (17 mg, 0.085 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 85%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.06 (s, 6H), 7.31-7.38 (m, 2H), 7.52 (td, J = 7.2, 1.2 Hz, 1H), 7.65 (d, J = 7.5 Hz, 1H), 8.17 (dt, J = 7.8, 0.9 Hz, 1H), 8.63 (dd, J = 5.7, 2.1 Hz, 1H), 8.98-9.00 (m, 1H); ¹³ C-NMR (CDCl ₃ ): δ8.2, 117.0, 123.8, 125.7, 129.0, 132.1, 134 , 149.5, 160.3, 165.1; ¹¹ B-NMR (CDCl ₃ ): δ0.8; HRMS (EI) C ₁₂ H ₁₂ BN ₂ ([M−H] ⁺ ): Theoretical value 195 1094, measured value 195.1103

(Example 2-22)
Under an argon atmosphere, trimethylaluminum (1.4 M, 0.79 ml, 0.21 mmol) was added to a toluene solution (2.0 ml) containing 2- (3-dibromoborylbenzothiophenyl) pyridine (200 mg, 0.53 mmol). In addition, the mixture was stirred at room temperature for 5 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator and purified by preparative thin layer chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (39);

Boron complex 31 (99 mg, 0.47 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 89%. Moreover, the light emission quantum yield in the solution was 57%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.15 (s, 6H), 7.23-7.27 (m, 1H), 7.34-7.43 (m, 2H), 7.58-7. 61 (m, 1H), 7.88-7.94 (m, 2H), 7.99-8.02 (m, 1H), 8.40-8.42 (m, 1H); ¹³ C-NMR (CDCl ₃ ): δ8.2, 117.6, 119.3, 123.3, 124.3, 125.6, 126.2, 132.7, 139.5, 140.5, 142.4, 146 ¹¹ B-NMR (CDCl ₃ ): δ1.0; HRMS (EI) C ₁₅ H ₁₄ BNS (M ⁺ ): Theoretical value 251.0940, Found value 251.0936

(Example 2-23)
Mixing a toluene solution (1.0 ml) containing 2,2 ′-(2,5-bisdibromoboryl-1,4-phenylene) dipyridine (57 mg, 0.10 mmol) and dichloromethane (1.0 ml) under an argon atmosphere To the solution was added trimethylaluminum (1.4M, 0.29 ml, 0.42 mmol) and stirred at room temperature for 5 minutes. The reaction solution was cooled to 0 ° C., water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. After concentrating the filtrate with a rotary evaporator, the produced white solid was collected by filtration and washed with hexane to obtain the following formula (40);

Boron complex 32 (22 mg, 0.71 mmol) represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 71%. The luminescence quantum yield in the solution was 46%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.09 (s, 12H), 7.36 (ddd, J = 7.8, 6.0, 1.2 Hz, 2H), 7.95-8.00 (m , 2H), 8.09-8.11 (m, 4H), 8.45 (d, J = 5.7 Hz, 2H); ¹³ C-NMR (CDCl ₃ ): δ 9.4, 118.4, 121 .3, 121.9, 137.7, 139.1, 142.2, 157.3; HRMS (EI) C ₂₀ H ₂₁ B ₂ N ₂ ([M−H] ⁺ ): Theoretical value 311.1891, Actual value 311.1881

(Example 2-24)
Under a nitrogen atmosphere, a mixed solvent of 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (5.8 g, 12 mmol) in toluene (25 ml) and dichloromethane (25 ml) was mixed with triethylaluminum in hexane. The solution (1M, 25 ml, 25.2 mmol) was added and stirred at room temperature for 1 hour. The reaction solution was added to ice water and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (41);

The boron complex 33 represented by (3.2 g, 8.4 mmol) was obtained with a yield of 70%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.42 (t, 6H), 0.49-0.56 (m, 2H), 0.72-0.80 (m, 2H), 7.40-7. 43 (m, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.74-7.75 (m, 1H), 7.81 (d, J = 8.0 Hz, 1H), 8.06-8.09 (m, 1H), 8.41-8.42 (m, 1H)

(Example 2-25)
Under a nitrogen atmosphere, a mixed solvent of a toluene solution (25 ml) containing 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (5.8 g, 12 mmol) and dichloromethane (25 ml) was mixed with triisobutylaluminum. Hexane solution (1M, 25 ml, 25.2 mmol) was added and stirred at room temperature for 1 hour. The reaction solution was added to ice water and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (42);

The boron complex 34 represented by (3.5 g, 8.0 mmol) was obtained in a yield of 67%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.34-0.36 (m, 6H), 0.50-0.54 (m, 8H), 0.54-0.97 (m, 4H), 41-7.43 (m, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.76-7.81 (m, 2H), 8.06-8.09 (m, 1H) ), 8.48-8.49 (m, 1H)

(Example 2-26)
Under a nitrogen atmosphere, a solution of phenyllithium in diethyl ether (1M, 31 ml, 35.2 mmol) is cooled to 0 ° C., and a solution of zinc chloride in diethyl ether (1M, 17 ml, 17 mmol) is added dropwise with stirring. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereto was added a toluene solution (80 ml) containing 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (3.8 g, 8 mmol), and the mixture was heated and stirred at 80 ° C. for 15 hours. After cooling to room temperature, the reaction solution was added to ice water and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (43);

A boron complex 35 represented by the formula (2.2 g, 4.61 mmol) was obtained in a yield of 58%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.16-7.26 (m, 10H), 7.45-7.48 (m, 1H), 7.69-7.71 (m, 1H), 7. 81 (d, J = 2.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 8.15-8.18 (m, 1H), 8.56 (d, J = 2 .0Hz, 1H)

(Example 2-27)
Under a nitrogen atmosphere, a solution of pentafluorophenyl magnesium bromide in diethyl ether (1M, 61.2 ml, 70.4 mmol) was cooled to 0 ° C., and a solution of zinc chloride in diethyl ether (1 M, 17 ml, 17 mmol) was stirred. Dripping. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereto was added a toluene solution (80 ml) containing 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (3.8 g, 8 mmol), and the mixture was heated and stirred at 80 ° C. for 15 hours. After cooling to room temperature, the reaction solution was added to ice water and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (44);

The boron complex 36 represented by (2.2 g, 4.61 mmol) was obtained with a yield of 58%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.16-7.26 (m, 10H), 7.45-7.48 (m, 1H), 7.69-7.71 (m, 1H), 7. 81 (d, J = 2.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 8.15-8.18 (m, 1H), 8.56 (d, J = 2 .0Hz, 1H)

(Example 2-28)
Under nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (159 mg, 0.3 mmol), trans-2-phenylvinylboronic acid (945 mg, 6.4 mmol), boron complex 27 (1.1 g, 3.1 mmol) To the mixture, 50 ml of tetrahydrofuran was added, and an aqueous solution in which 750 mg of sodium hydroxide was dissolved in 13 ml of distilled water was added, and the mixture was stirred with heating at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (45);

A boron complex 37 represented by the formula (1.1 g, 2.8 mmol) was obtained in a yield of 88%. Moreover, the light emission quantum yield in the solution was 90%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.10-7.76 (m, 15H), 7.78-7.82 (m, 2H), 7.90 (d, J = 8.0 Hz, 1H), 8.09-8.12 (m, 1H), 8.47-8.48 (m, 1H)

(Example 2-29)
Under nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (204 mg, 0.4 mmol), trans-2-phenylvinylboronic acid (1213 mg, 8.2 mmol), boron complex 33 (1.1 g, 4 mmol) and tetrahydrofuran Was added, and an aqueous solution in which 960 mg of sodium hydroxide was dissolved in 18 ml of distilled water was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (46);

A boron complex 38 represented by the formula (1.5 g, 3.5 mmol) was obtained in a yield of 88%. Moreover, the light emission quantum yield in the solution was 90%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.50 (t, J = 8.0 Hz, 6H), 0.59-0.64 (m, 2H), 0.82-0.88 (m, 2H), 7.10-7.58 (m, 15H), 7.78-7.82 (m, 2H), 7.91 (d, J = 8.0 Hz, 1H), 8.10-8.13 (m , 1H), 8.38-8.39 (m, 1H)

(Example 2-30)
Under nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (163 mg, 0.32 mmol), trans-2-phenylvinylboronic acid (970 mg, 6.56 mmol), boron complex 34 (1.4 g, 3.2 mmol) To the mixture, 50 ml of tetrahydrofuran was added, and an aqueous solution in which 770 mg of sodium hydroxide was dissolved in 15 ml of distilled water was added, and the mixture was stirred with heating at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (47);

A boron complex 39 represented by the formula (1.3 g, 2.7 mmol) was obtained in a yield of 84%. The luminescence quantum yield in the solution was 89%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.38 (d, J = 8.0 Hz, 6H), 0.56-0.64 (m, 8H), 0.90-0.95 (m, 2H), 1.04-1.55 (m, 2H), 7.16-7.59 (m, 15H), 7.77-7.82 (m, 2H), 7.90 (d, J = 8.0 Hz) , 1H), 8.10-8.11 (m, 1H), 8.44-8.45 (m, 1H)

(Example 2-31)
Under a nitrogen atmosphere, 30 ml of tetrahydrofuran was added to bis (tri-tert-butylphosphine) palladium (102 mg, 0.2 mmol), trans-2-phenylvinylboronic acid (607 mg, 4.1 mmol), boron complex 35 (954 mg, 2 mmol). Furthermore, an aqueous solution in which 480 mg of sodium hydroxide was dissolved in 8 ml of distilled water was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (48);

The boron complex 40 represented by (800 mg, 1.53 mmol) was obtained with a yield of 77%.
The luminescence quantum yield in the solution was 79%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 6.9-7.52 (m, 20H), 7.83-7.85 (m, 2H), 7.98 (d, J = 8.0 Hz, 1H), 8.18-8.20 (m, 1H), 8.50-8.51 (m, 1H)

(Example 2-32)
Under a nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (204 mg, 0.4 mmol), the following formula (49);

60 ml of tetrahydrofuran was added to boronic acid ester (3 g, 8.2 mmol) and boron complex 27 (1.4 g, 4 mmol), and an aqueous solution obtained by dissolving 960 mg of sodium hydroxide in 16 ml of distilled water was added. The mixture was heated and stirred at 3 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (50);

The boron complex 41 represented by (2.3 g, 3.4 mmol) was obtained with a yield of 85%. The luminescence quantum yield in the solution was 92%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.30-7.36 (m, 4H), 7.43-7.53 (m, 8H), 7.66-7.69 (m, 3H), 7. 78-7.80 (m, 2H), 7.90-7.92 (m, 2H), 7.96-8.03 (m, 4H), 8.11-8.20 (m, 5H), 8.28-8.31 (m, 1H), 8.77-8.78 (m, 1H)

(Example 2-33)
In a nitrogen atmosphere, a solution of zinc chloride in diethyl ether (1M, 11.9 ml, 11.9 mmol) was cooled to 0 ° C., and 4-propylphenylmagnesium bromide in tetrahydrofuran (THF) (0.5 M, 49.9 ml) was added thereto. , 24.9 mmol) is added dropwise with stirring. After stirring at room temperature for 1 hour, it was diluted with toluene (30 ml), and 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (3.3 g, 6.9 mmol) was added thereto in one portion. After stirring with heating at 80 ° C. for 15 hours, the mixture was cooled to room temperature, water was added, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography (hexane: dichloromethane = 1: 1) to obtain the following formula (51);

The boron complex 42 represented by (350 mg, 0.62 mmol) was obtained in a yield of 9%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.94 (t, J = 7.2 Hz, 6H), 1.62 (sec, J = 7.6 Hz, 4H), 2.53 (t, J = 7.8 Hz) 4H), 7.03-7.09 (m, 8H), 7.45 (dd, J = 8.2, 1.8 Hz, 1H), 7.69 (d, J = 7.8 Hz, 1H) , 7.86 (d, J = 2.0 Hz, 1H), 7.87 (dd, J = 8.8, 0.8 Hz), 8.13 (dd, J = 8.8, 2.0 Hz, 1H) )

(Example 2-34)
THF containing 4-iodo-2-fluorobromobenzene (8.0 g, 26.6 mmol), bispinacolatodiboron (5.1 g, 39.9 mmol), copper iodide (0.51 g, 2.7 mmol) ( 106 ml) Sodium hydride (0.96 g, 39.9 mmol) was added in one portion at room temperature with nitrogen flowing through the solution. The reaction solution was stirred at room temperature for 12 hours under a nitrogen atmosphere, and then the reaction was stopped with a saturated aqueous ammonium chloride solution while cooling with ice. The mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator. The residue was purified by column chromatography (ethyl acetate: hexane = 1: 10) to obtain 5.1 g of 2-fluoro-4-bromophenylpinacolatoborane. This, 2-bromopyridine (5.1 g, 21.4 mmol) and tetrakistriphenylphosphine palladium (740 mg, 0.64 mmol) were dissolved in toluene (93 ml) and ethanol (23 ml), and sodium carbonate (4.8 g, An aqueous solution in which 44.9 mmol) was dissolved in H ₂ O (23 ml) was added and stirred while heating at 100 ° C. for 24 hours. The reaction solution was diluted with ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and filtered. The filtrate was concentrated with a rotary evaporator, and the residue was purified by silica gel column chromatography to give 2- (2-fluoro-4-bromophenyl) -5-bromopyridine (4.3 g, 12.8 mmol) in a yield of 85%. Obtained.
Next, 2- (2-fluoro-4-bromophenyl) -5-bromopyridine (1.0 g, 4.3 mmol) and diisopropylethylamine (0.74 ml, 4.3 mmol) were added to 1,2-dichloroethane (43 ml). Dissolve and slowly add dropwise a solution of boron tribromide in dichloromethane (1.0 M, 12.8 ml, 12.8 mmol) while cooling to −20 ° C. The reaction solution was stirred for 1 hour at room temperature and then heated and stirred at 70 ° C. for 12 hours. The reaction was stopped by adding water, followed by extraction with dichloromethane. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The filtrate was concentrated on a rotary evaporator, and the resulting solid was washed with hexane to obtain 1.1 g of 2- (2-dibromoboryl-4-bromo-6-fluorophenyl) -5-bromopyridine (2.2 mmol). Obtained. This was dissolved in toluene, a hexane solution of 25% by mass trioctylaluminum (10.1 ml, 4.8 mmol) was added at room temperature, and the mixture was stirred for 3 hours. Water was added to stop the reaction, followed by extraction with dichloromethane, washing with saturated brine, drying over magnesium sulfate, and filtration. The residue obtained by concentrating the filtrate was purified by silica gel column chromatography (hexane: chloroform = 2: 1) to obtain the following formula (52);

(Wherein ⁿ C ₈ H ₁₇ represents an n-octyl group) 2- (2-octylboryl-4-bromo-6-fluorophenyl) -5-bromopyridine (boron complex 43; 0 .50 g, 8.8 mmol) was obtained with a yield of 40%.
The reaction formula of this reaction is shown in FIG.
Moreover, the physical property value of the obtained boron complex 43 was as follows.
¹ H-NMR (CDCl ₃ ): δ 0.47-0.62 (m, 4H), 0.71-0.77 (m, 4H), 0.84 (t, J = 7.0 Hz, 6H), 1.10-1.25 (m, 20H), 7.12 (dd, J = 10.2, 0.9 Hz, 1H), 7.49 (d, J = 1.2 Hz, 1H), 8.04 (D, J = 8.4 Hz), 8.10 (dd, J = 8.8, 2.0 Hz, 1H), 8.44 (d, J = 2.0 Hz, 1H)

(Example 2-35)
Under a nitrogen atmosphere, boron complex 28 (54.9 mg, 0.10 mmol), phenylboronic acid (24.4 mg, 0.20 mmol), tetrakistriphenylphosphine palladium (0) (5.8 mg, 0.005 mmol), sodium carbonate (21.2 mg, 0.20 mmol), toluene 1.0 ml and water 0.2 ml were stirred at 90 ° C. for 24 hours. Water was added, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with ethyl acetate. The organic layers were combined and washed once with water and once with a saturated aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was isolated and purified using silica gel chromatography, and the following formula (53);

A boron complex 44 (44.8 mg, 0.082 mmol) represented by the formula ( ^{where n} Oct represents an octyl group) was obtained in a yield of 82%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.58-1.22 (m, 34H), 7.35-7.40 (m, 1H), 7.46-7.58 (m, 6H), 7. 63-7.67 (m, 2H), 7.72-7.75 (m, 2H), 7.87-7.93 (m, 2H), 8.01 (d, J = 8.4 Hz, 1H ), 8.16 (dd, J = 8.3, 2.0 Hz, 1H), 8.59 (d, J = 2.1 Hz, 1H)

(Example 2-36)
Under a nitrogen atmosphere, boron complex 28 (27.5 mg, 0.050 mmol), diphenylamine (25.4 mg, 0.15 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2.6 mg, 0.25 mmol). 0025 mmol), bis (tri-tert-butylphosphine) palladium (4.1 mg, 0.02 mmol), sodium tert-butoxide (48.1 mg, 0.50 mmol), and 1.5 ml of toluene heated at 100 ° C. for 24 hours. Stir. Water was added, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with ethyl acetate. The organic layers were combined and washed once with water and once with a saturated aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was isolated and purified using silica gel chromatography, and the following formula (54);

A boron complex 45 (27.0 mg, 0.037 mmol) represented by the formula ( ^{where n} Oct represents an octyl group) was obtained in a yield of 74%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.31-1.32 (m, 34H), 6.91 (dd, J = 8.1, 2.1 Hz, 1H), 7.01-7.06 (m , 2H), 7.12-7.20 (m, 11H), 7.25-7.37 (m, 10 Hz), 7.56-7.64 (m, 1H), 8.05 (d, J = 1.5Hz, 1H)

(Example 2-37)
Under a nitrogen atmosphere, boron complex 28 (54.9 mg, 0.1 mmol) is dissolved in 0.5 ml of tetrahydrofuran and cooled to −78 ° C. A normal butyl lithium hexane solution (1.6 M, 135 μl, 0.21 mmol) was added dropwise thereto and stirred for 1 hour. Isopropoxy pinacol borane (74.4 mg, 0.40 mmol) was added and stirred at room temperature for 12 hours. Water was added, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with ethyl acetate. The organic layers were combined and washed once with water and once with a saturated aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product is isolated and purified using recycled preparative GPC, and the following formula (55):

A boron complex 46 (35.0 mg, 0.054 mmol) represented by the formula ( ^{where n} Oct represents an octyl group) was obtained in a yield of 54%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.54-1.22 (m, 34H), 1.38-1.39 (m, 24H), 7.74 (dd, J = 7.5, 1.2 Hz) , 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.94 (d, J = 8.1 Hz, 1H), 8.09 (s, 1H), 8.28 (dd, J = 7.8, 1.2 Hz, 1H), 8.67 (s, 1H)

(Example 2-38)
Under nitrogen atmosphere, boron complex 28 (54.9 mg, 0.1 mmol) is dissolved in 0.5 ml of diethyl ether and cooled to −78 ° C. A normal butyl lithium hexane solution (1.6 M, 71 μl, 0.11 mmol) was added dropwise thereto and stirred for 1 hour. Isopropoxy pinacol borane (37.2 mg, 0.20 mmol) was added and stirred at room temperature for 12 hours. Water was added, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with ethyl acetate. The organic layers were combined and washed once with water and once with a saturated aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product is isolated and purified using recycle preparative GPC, and the following formula (56):

Boron complex 47 (38.4 mg, 0.064 mmol) represented by the formula ( ^{where n} Oct represents an octyl group) was obtained in a yield of 64%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.48-1.33 (m, 34H), 1.39 (s, 12H), 7.40 (dd, J = 8.4, 1.5 Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.76 (d, J = 1.5 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 8.29 (d , J = 7.8 Hz, 1H), 8.64 (s, 1H)

(Example 2-39)
Tetrahydrofuran was added to bis (tri-tert-butylphosphine) palladium (46.0 mg, 0.09 mmol), phenylboronic acid (225 mg, 1.85 mmol), boron complex 36 (591.2 mg, 0.9 mmol) under a nitrogen atmosphere. 15 ml was added, and an aqueous solution in which 216 mg of sodium hydroxide was dissolved in 4 ml of distilled water was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (57);

The boron complex 48 represented by (470 mg, 0.72 mmol) was obtained with a yield of 80%. The luminescence quantum yield in the solution was 96%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.36-7.55 (m, 8H), 7.63-7.66 (m, 3H), 7.94-7.96 (m, 2H), 8. 10-8.13 (m, 1H), 8.32-8.35 (m, 1H), 8.73 (s, 1H)

(Example 2-40)
Under a nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (46.0 mg, 0.09 mmol), trans-2-phenylvinylboronic acid (273 mg, 1.85 mmol), boron complex 36 (591.2 mg, 0.0. 9 mmol), 15 ml of tetrahydrofuran was added, an aqueous solution in which 216 mg of sodium hydroxide was dissolved in 4 ml of distilled water was added, and the mixture was stirred with heating at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (58);

A boron complex 49 represented by the formula (552 mg, 0.78 mmol) was obtained in a yield of 87%. Moreover, the light emission quantum yield in the solution was 70%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.03-7.29 (m, 5H), 7.34-7.43 (m, 5H), 7.53-7.59 (m, 5H), 7. 82 (s, 1H), 7.84 (s, 1H), 8.00 (d, J = 8.0 Hz, 1H), 8.29-8.31 (m, 1H), 8.51 (s) , 1H)

(Example 2-41)
Under a nitrogen atmosphere, 250 ml of diethyl ether is added to 2-bromobiphenyl (12.1 g, 52.2 mmol) and cooled to -78 ° C. A hexane solution of normal butyl lithium (1.65 M, 32 ml, 52.8 mmol) is added dropwise thereto and stirred for 1 hour. A solution of zinc chloride in diethyl ether (1M, 25.2 ml, 25.2 mmol) is added dropwise with stirring. 200 ml of toluene is added here and heated to 85 ° C., and diethyl ether is completely distilled off. The mixture was heated to 110 ° C. and stirred for 2 hours, 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (5.8 g, 12 mmol) was added thereto, and the mixture was heated and stirred at 110 ° C. for 96 hours. After cooling to room temperature, the reaction solution was added to ice water and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated with a rotary evaporator and purified by silica gel chromatography to obtain the following formula (59);

The boron complex 50 represented by the formula (2.5 g, 3.97 mmol) was obtained in a yield of 33%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 6.41 (br, 4H), 6.81-6.91 (m, 8H), 7.16-7.24 (m, 4H), 7.26-7. 30 (m, 3H), 7.44 (d, J = 1.2 Hz, 1H), 7.55-7.57 (m, 1H), 7.61-7.62 (m, 1H), 7. 65-7.68 (m, 1H)

(Example 2-42)
Under a nitrogen atmosphere, bis (tri-tert-butylphosphine) palladium (46.0 mg, 0.09 mmol), trans-2-phenylvinylboronic acid (273.0 mg, 1.85 mmol), boron complex 50 (566.3 mg, 0.9 mmol), 15 ml of tetrahydrofuran was added, and an aqueous solution in which 216 mg of sodium hydroxide was dissolved in 4 ml of distilled water was added, followed by heating and stirring at 70 ° C. for 3 hours. After cooling to room temperature, the solvent is concentrated, purified by silica gel chromatography (toluene), and recrystallized from toluene to give the following formula (60);

The boron complex 51 represented by (500 mg, 0.74 mmol) was obtained with a yield of 82%. Moreover, the light emission quantum yield in the solution was 78%.
The physical property values were as follows.
¹ H-NMR (CDCl ₃ ): δ 6.44-6.54 (m, 4H), 6.74-6.93 (m, 8H), 7.07 (s, 2H), 7.16-7. 20 (m, 2H), 7.26-7.50 (m, 17H), 7.54-7.56 (m, 2H), 7.65-7.67 (m, 2H), 7.74- 7.77 (m, 1H)

(Example 3)
Under an argon atmosphere, 0.5 ml of dichloromethane was dissolved in 2-phenylpyridine (77.6 mg, 0.5 mmol), and 0.5 ml of a 1.0 M solution of boron tribromide in dichloromethane was added thereto at 0 ° C. Stir for 1 hour. To this was added 935 μl of 1.07M trimethylaluminum solution, and the mixture was further stirred at room temperature for 1 hour. Quenched by adding water at 0 ° C., extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution, the organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The resulting mixture was subjected to preparative thin layer chromatography (hexane: dichloromethane = 1: 1). The following formula (61):

A boron complex 52 represented by the formula (wherein Me represents a methyl group) was obtained in a yield of 65%.
The reaction formula of this reaction is shown in FIG.

(Example 4-1)
Following formula (62);

B8 dibromide represented by (137.3 mg, 0.25 mmol), the following formula (63);

F8 boronic acid diester (140.3 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. To this was added an aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated under reflux at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (64);

The boron containing polymer F8B8 represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8B8 was 80000. Moreover, the light emission quantum yield in a solution was 87%.

(Example 4-2)
B8 dibromide represented by the formula (62) (137.3 mg, 0.25 mmol), the following formula (65);

Bithiophene boronic acid diester (147.4 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) represented by the formula (1) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under nitrogen flow. . An aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water was added thereto, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated and refluxed at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (66):

The boron containing polymer B8T2 represented by these was obtained. The weight average molecular weight of the boron-containing polymer B8T2 was 40000. Moreover, the light emission quantum yield in a solution was 29%.

(Example 4-3)
B8 dibromide represented by the formula (62) (137.3 mg, 0.25 mmol), the following formula (67);

The boronic acid diester (112.1 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) represented by the formula (1) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. An aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water was added thereto, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated and refluxed at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (68);

The boron containing polymer B8P6 represented by these was obtained. The weight average molecular weight of the boron-containing polymer B8P6 was 60000. Moreover, the light emission quantum yield in a solution was 66%.

(Example 4-4)
B8 dibromide (137.3 mg, 0.25 mmol) represented by the formula (62), the following formula (69);

The boronic acid diester (124.4 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) represented by formula (1) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. An aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water was added thereto, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated and refluxed at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (70);

The boron containing polymer B8Cz represented by these was obtained. The weight average molecular weight of the boron-containing polymer B8Cz was 22,000. Moreover, the light emission quantum yield in a solution was 74%.

(Example 4-5)
B8 dibromide represented by the formula (62) (137.3 mg, 0.25 mmol), the following formula (71);

The boronic acid diester (139.0 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) represented by the formula (1) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. An aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water was added thereto, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated and refluxed at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (72);

The boron containing polymer B8TPA represented by these was obtained. The weight average molecular weight of the boron-containing polymer B8TPA was 18000. Moreover, the light emission quantum yield in a solution was 60%.

(Example 4-6)
B8 dibromide represented by the formula (62) (137.3 mg, 0.25 mmol), the following formula (73);

The boronic acid diester (227.3 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) represented by the formula were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. An aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water was added thereto, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated and refluxed at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (74);

A boron-containing polymer B8FspiroTPA represented by The weight average molecular weight of the boron-containing polymer B8FspiroTPA was 5500.

(Example 4-7)
B8 dibromide represented by the formula (62) (137.3 mg, 0.25 mmol), the following formula (75);

B8 diester (140.5 mg, 0.251 mmol) and tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) were dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. To this was added an aqueous solution prepared by dissolving ammonium carbonate (240.4 mg, 0.8 mmol) in 0.75 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete deaeration. This was heated under reflux at 115 ° C. for 17 hours, and bromobenzene (39.3 mg, 0.25 mmol) was added for end-capping, and the mixture was stirred for 1 hour. Further, phenylboronic acid (30.5 mg, 0.25 mmol) was added. added. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (76);

The boron containing polymer PB8 represented by these was obtained. The weight average molecular weight of the boron-containing polymer PB8 was 11,000. Moreover, the light emission quantum yield in a solution was 49%.

(Example 4-8)
Following formula (77);

BPhPr dibromide (350 mg, 0.62 mmol), F8 boronic acid diester (348 mg, 0.62 mmol) represented by formula (63), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ dba ₃ 14.3 mg, 0.016 mmol), tricyclohexylphosphine (17.5 mg, 0.062 mmol), cesium carbonate (1.22 g, 3.74 mmol), pure water (0.09 ml) in THF (9.3 ml); The mixture was dissolved and heated and stirred at 65 ° C. for 48 hours under a nitrogen atmosphere. To end-clamp, bromobenzene (127 mg, 0.81 mmol) was added and stirred for 5 hours, and phenylboronic acid (357 mg, 2.93 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (78);

The boron containing polymer F8BPhPr represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8BPhPr was 10700.

(Example 4-9)
Following formula (79);

B8F dibromide represented by formula (280 mg, 0.49 mmol) and F8 boronic acid diester represented by formula (63) (281 mg, 0.50 mmol) were dissolved in toluene (3 ml) and THF (3 ml), And stirred for 10 minutes at room temperature. Here, mixing of trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich; 20 mg), 25% by mass tetraethylammonium hydroxide (Et ₄ NOH) aqueous solution (0.83 ml) and distilled water (0.75 ml) An aqueous solution was added, and the mixture was further stirred at room temperature for 20 minutes under an argon atmosphere to complete deaeration. Tetrakistriphenylphosphine palladium (8.6 mg, 0.007 mmol) was added thereto, followed by stirring with heating for 48 hours while refluxing at 115 ° C. To end-clamp, bromobenzene (101 mg, 0.64 mmol) was added and stirred for 5 hours, and phenylboronic acid (283 mg, 2.32 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (80);

The boron containing polymer F8B8F represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8B8F was 126000.

(Example 4-10)
Following formula (81);

BC6F5 dibromide represented by the formula (337 mg, 0.51 mmol) and F8 boronic acid diester represented by the formula (63) (292 mg, 0.52 mmol) were dissolved in toluene (3 ml) and THF (3 ml), And stirred for 10 minutes at room temperature. To this, a mixed aqueous solution of Aliquat 336 (21 mg), 25 mass% Et ₄ NOH aqueous solution (0.86 ml) and distilled water (0.75 ml) was added, and the mixture was further stirred at room temperature for 20 minutes in an argon atmosphere to complete deaeration. I let you. Tetrakistriphenylphosphine palladium (8.9 mg, 0.007 mmol) was added thereto, and the mixture was heated and stirred for 48 hours while refluxing at 115 ° C. To end-clamp, bromobenzene (105 mg, 0.67 mmol) was added and stirred for 5 hours, and phenylboronic acid (294 mg, 2.41 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (82);

The boron containing polymer F8BC6F5 represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8BC6F5 was 126000.

(Example 4-11)
B8 dibromide represented by formula (62) (241 mg, 0.44 mmol), F8 boronic acid diester represented by formula (63) (500 mg, 0.90 mmol), the following formula (83);

4,7-dibromobenzothiadiazole (129 mg, 0.44 mmol) was dissolved in 11 ml of toluene and stirred at room temperature for 10 minutes in a nitrogen atmosphere. To this was added an aqueous solution prepared by dissolving tetraethylammonium carbonate (1.02 g, 5.37 mmol) in 3 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes in a nitrogen atmosphere to complete deaeration. Tetrakistriphenylphosphine palladium (10.3 mg, 0.009 mmol) was added thereto, and then the mixture was heated and stirred for 48 hours while refluxing at 115 ° C. To end-capping, bromobenzene (183 mg, 1.16 mmol) was added and stirred for 5 hours, and phenylboronic acid (513 mg, 4.21 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (84);

The boron containing polymer F8B8BT represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8B8BT was 10800.

(Example 4-12)
B8 dibromide represented by formula (62) (290 mg, 0.71 mmol), F8 boronic acid diester represented by formula (63) (500 mg, 0.90 mmol), the following formula (85);

2,7-dibromodibenzothiophene dioxide (131 mg, 0.35 mmol) was dissolved in 11 ml of toluene and stirred at room temperature for 10 minutes in a nitrogen atmosphere. To this was added an aqueous solution prepared by dissolving tetraethylammonium carbonate (1.02 g, 5.37 mmol) in 3 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes in a nitrogen atmosphere to complete deaeration. Tetrakistriphenylphosphine palladium (15.5 mg, 0.013 mmol) was added thereto, followed by heating and stirring for 48 hours while refluxing at 115 ° C. To end-capping, bromobenzene (183 mg, 1.16 mmol) was added and stirred for 5 hours, and phenylboronic acid (513 mg, 4.21 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (86);

The boron containing polymer F8B8DBThO2 represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8B8DBThO2 was 8900.

(Example 4-13)
B8 dibromide represented by formula (62) (389 mg, 0.71 mmol), F8 boronic acid diester represented by formula (63) (500 mg, 0.90 mmol), the following formula (87);

N, N-bis (4-dibromophenyl) -4-isobutylaniline (65 mg, 0.14 mmol) was dissolved in 11 ml of toluene and stirred at room temperature for 10 minutes in a nitrogen atmosphere. To this was added an aqueous solution prepared by dissolving tetraethylammonium carbonate (1.02 g, 5.37 mmol) in 3 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes in a nitrogen atmosphere to complete deaeration. Tetrakistriphenylphosphine palladium (15.5 mg, 0.013 mmol) was added thereto, followed by heating and stirring for 48 hours while refluxing at 115 ° C. To end-capping, bromobenzene (183 mg, 1.16 mmol) was added and stirred for 5 hours, and phenylboronic acid (513 mg, 4.21 mmol) was further added and stirred for 5 hours. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (88);

The boron containing polymer F8B8BT represented by these was obtained. The weight average molecular weight of the boron-containing polymer F8B8BT was 25400.

(Example 4-14)
Following formula (89);

B8 boronic acid diester (161.6 mg, 0.251 mmol) represented by the following formula (90);

BT dibromide represented by (73.5 mg, 0.25 mmol) was dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes in a nitrogen atmosphere. To this was added an aqueous solution prepared by dissolving tetraethylammonium carbonate (240.4 mg, 0.75 mmol) in 0.75 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes in a nitrogen atmosphere to complete deaeration. Tetrakistriphenylphosphine palladium (2.9 mg, 0.0025 mmol) was added thereto, followed by stirring with heating for 18 hours while refluxing at 115 ° C. To end-clamp, bromobenzene (92 mg, 0.58 mmol) was added and stirred for 1 hour, and further phenylboronic acid (256 mg, 2.11 mmol) was added and stirred for 1 hour. The reaction solution was allowed to cool to room temperature, diluted with toluene, washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (91);

The boron-containing polymer B8BT represented by this was obtained. The weight average molecular weight of the boron-containing polymer B8BT was 118000.

(Example 4-15)
Boron complex 50 represented by formula (59) (440.4 mg, 0.7 mmol), F8 boronic acid diester represented by formula (63) (392.8 mg, 0.704 mmol), tetrakistriphenylphosphine palladium (8 0.1 mg, 0.007 mmol) was dissolved in 3 ml of toluene and stirred at room temperature for 10 minutes under a nitrogen flow. To this was added an aqueous solution prepared by dissolving ammonium carbonate (673.1 mg, 2.1 mmol) in 2.1 ml of distilled water, and the mixture was further stirred at room temperature for 20 minutes under a nitrogen flow to complete degassing. This was heated under reflux at 115 ° C. for 17 hours, and bromobenzene (117.9 mg, 0.75 mmol) was added for end-capping, followed by stirring for 4 hours. Further, phenylboronic acid (91.5 mg, 0.75 mmol) was added. The mixture was further stirred for 4 hours. The solution was allowed to cool to room temperature, and the toluene solution was separated and washed once with hydrochloric acid and twice with pure water, and the organic layer was concentrated to about several ml. The concentrated solution was dropped into 300 ml of methanol and stirred for 10 minutes as it was, and the resulting precipitate was collected by filtration. By repeating the same purification process three times in total and drying the solid under reduced pressure, the following formula (92);

The boron containing polymer F8BBPh represented by this was obtained. The weight average molecular weight of the boron-containing polymer F8BBPh was 120,000.

(Example 5)
[1] First, a commercially available transparent glass substrate with FTO having an average thickness of 2.3 mm was prepared.
[2] Next, the FTO electrode (cathode) was etched with zinc powder and 4N hydrochloric acid to form a pattern.
[3] Next, a titanium oxide (TiO ₂ ) layer (electron-injecting metal oxide layer) having an average thickness of 100 nm was formed on the FTO electrode by spray pyrolysis. Specifically, Journal of European Ceramic Society, 1999, Vol. 19, p. 903 or Ceramic Transactions, 2000, 109, p. 473 etc., diisopropoxy / bisacetylacetonato titanium solution and ethanol were mixed at a mass ratio of 1:10 and spray-coated on the FTO substrate described in the above [2] heated at 450 ° C.
[4] Next, the boron-containing polymer F8B8 obtained in Example 4-1 was dissolved in xylene at 0.5% by mass, and spin-coated on the TiO ₂ layer (electron-injecting metal oxide layer). After applying by the method (2000 rpm), it was dried. The drying condition of the liquid material was room temperature in the atmosphere. As a result, a light emitting layer was obtained.
[5] Molybdenum oxide (MoO ₃ ) was vapor-deposited with an average thickness of 10 nm on the light-emitting layer using a vacuum vapor deposition apparatus to produce a hole-injecting metal oxide layer.
[6] In the continuous process of [5] above, gold (Au) (anode) was vapor-deposited with an average thickness of 30 nm to obtain an element. The device was able to confirm light emission from around 10V.

Claims (10)

A luminescent material comprising a boron-containing compound having a boron atom and a double bond,
The boron-containing compound has the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent. The luminescent material according to claim 1, wherein the boron-containing compound has an emission quantum yield of 20 to 100%. In the boron-containing compound, R ¹ and R ² in the formula (1) are the same or different and are a linear or branched hydrocarbon group having 1 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. The luminescent material according to claim 1, wherein the luminescent material is a hydrocarbon group. A light-emitting device formed using the light-emitting material according to claim 1. A boron-containing compound having a boron atom and a double bond,
The boron-containing compound has the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² may be the same or different and each represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² may be bonded to the ring structure forming the dotted arc portion. R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent substituent.) At least one of the above X ¹ and X ² has a double bond at the end. One of the two atoms having a structure connected by Boron-containing compound, characterized by having a structure bonded with the ring structure forming a circular arc portion of the dotted line. A boron-containing polymer obtained by polymerizing a monomer component containing a boron-containing compound having a boron atom and a double bond,
The boron-containing compound has the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent, and the boron-containing compound is represented by X ¹ , X ² in the formula (1). , At least one of R ¹ and R ² has a reactive group A boron-containing polymer, which is a substituent. In the boron-containing polymer, R ¹ and R ² in the formula (1) are the same or different, and a linear or branched hydrocarbon group having 1 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. The boron-containing polymer according to claim 6, which is a hydrocarbon group of formula. The boron-containing polymer according to claim 6 or 7, wherein the boron-containing polymer is used for forming a light emitting device. A light-emitting device formed using the boron-containing polymer according to claim 6. Following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom. The dotted line part in the skeleton part connecting the boron atom and the nitrogen atom is at least It represents that a pair of atoms are connected by a double bond, and the double bond may be conjugated with a ring structure.The arrow from the nitrogen atom to the boron atom indicates that the nitrogen atom is coordinated to the boron atom. X ¹ and X ² are the same or different and each represents a hydrogen atom or a monovalent substituent serving as a substituent of the ring structure, and a plurality of X ¹ and X ² are bonded to the ring structure forming the dotted arc portion. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a monovalent substituent.)
The production method comprises the following formula (I):

(In the formula, a dotted arc indicates that a ring structure is formed together with a part of the skeleton part that connects the hydrogen atom and nitrogen atom. The dotted line in the skeleton part that connects the hydrogen atom and nitrogen atom) The moiety represents that at least one pair of atoms is bonded by a double bond, and the double bond may be conjugated to a ring structure, and X ¹ and X ² may be the same or different and represent a hydrogen atom or a ring And a compound represented by the following formula (II): a monovalent substituent serving as a substituent of the structure may be bonded to a ring structure forming a dotted arc part).

(In formula, Q is the same or different and represents a bromine atom or an iodine atom.) The manufacturing method of the boron containing compound characterized by making the process with the compound represented by essential is essential.

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