JP2013194039A - Boron-including compound and process for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic boron compound capable of stably delivering performance as a characteristic of electronic element material, in addition to a low energy level of LUMO (Lowest Unoccupied Molecular Orbital).SOLUTION: A boron-including compound has a heterocyclic structure including a boron atom, and is shown by formula (1).

Description

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

An organoboron compound having a boron atom in its structure is attracting attention as a functional electronic element material such as an organic semiconductor or an organic EL element because of electronic characteristics resulting from an electronic state in the molecular orbital of the boron atom. Among functional electronic devices, in the field of organic semiconductors, many materials have been proposed and developed for p-type organic semiconductors including poly (3-hexylthiophene) (P3HT). On the other hand, development of n-type organic semiconductors typified by fullerene derivatives has been delayed for various reasons. In particular, since few polymer n-type organic semiconductors suitable for the coating process are known, rapid development is desired, and development of organoboron compounds having various structures and research on properties are actively conducted. Yes.

As a conventional organic boron compound, it has been shown that an organic boron compound having a structure of a fluorene derivative-type boron-containing compound has a property of capturing a fluorine atom and changing its color (for example, see Non-Patent Document 1). . Moreover, the synthesis | combination of the high molecular compound which used the fluorene derivative type boron containing compound and the fluorene derivative type boron containing compound as a raw material, and the measurement of the fluorescence spectrum are performed (for example, refer patent documents 1-3). Furthermore, it is disclosed that a fluorene derivative-type boron-containing compound was synthesized and the oxidation-reduction potential was measured by cyclic voltammetry (see, for example, Patent Document 4). Furthermore, an organic electroluminescent element containing a polymer transport material having a repeating unit composed of a structural site derived from an organoboron compound and an arylene group or heteroarylene group is disclosed (for example, see Patent Document 5).

Japanese Patent No. 3817632 Japanese Patent No. 4196747 JP 2004-162011 A Japanese Patent No. 4139904 JP 2011-14711 A

Three members of Shigehiro Yamaguchi, “Journal of the American Chemical Society”, 2002, No. 124, p. 8816-8817

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 functional electronic element materials such as organic semiconductors and organic EL elements are expected as described above. In addition to low LUMO energy levels, materials used as device materials are also required to be able to exhibit their performance stably with little change in physical properties.
As described above, organic boron compounds having various structures have been disclosed, and some of them have been evaluated for performance as electronic device materials. However, these conventional organoboron compounds cannot be said to be sufficient in terms of stability for use as electronic device materials. Organic semiconductors do not use rare metals as materials, and because they have merits that inorganic semiconductors do not have, such as being able to form semiconductor layers by coating, they should exhibit excellent electrical characteristics stably. There is a high expectation for an organic semiconductor that can be used, and there is a demand for the development of a compound as an organic semiconductor material that can exhibit such high performance.

The present invention has been made in view of the above situation, and an object thereof is to provide an organoboron compound capable of stably exhibiting characteristics as an electronic device material in addition to a low LUMO energy level. And

The present inventor has examined the cause of the fact that conventional organoboron compounds are not sufficient in terms of stability of characteristics, and these conventional organoboron compounds are all three-coordinate compounds with respect to boron. It was thought that the stability of the characteristics could be improved by using a 4-coordinate compound in advance. Then, various studies are made on compounds that are tetracoordinate to boron and have a low LUMO energy level, and have a double bond in a cyclic skeleton having a boron atom, and the skeleton has at least two rings. In addition to forming a part of the structure, the inventors have conceived a compound having a structure in which two specific atoms are further bonded or coordinated to a boron atom and the two specific atoms are bonded via a linking group. The present inventor has found that even when this compound is exposed to a solution containing a fluorine ion having a low LUMO energy level and coordinating with a boron atom to cause a color change in Non-Patent Document 1, It is a compound that can maintain characteristics as an element material and is excellent in terms of stability of characteristics, and this compound is an organic semiconductor or an organic EL element. It is found that the compound can be suitably used as a material of a HOILED (hybrid organic-inorganic light-emitting diode) element having an advantage of higher resistance to oxygen and water than the above, and can solve the above-mentioned problems in an excellent manner. The present invention has been conceived and reached the present invention.

That is, the present invention is a boron-containing compound having a heterocyclic structure containing a boron atom,
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 a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Alternatively, it represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of each may be bonded to a ring structure forming a dotted arc part.The arrow from U to a boron atom indicates that the U atom is a boron atom The solid arc connecting T and U indicates that T and U are connected via a connecting portion having at least one atom, and the connecting portion is a ring. It may have a structure, and a part or all of the connecting portion and U are A ring structure composed of one or a plurality of rings may be formed, T represents any of a sulfur atom and an oxygen atom, and U represents any of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ³ and X ⁴ may be the same or different and each represents a hydrogen atom or a monovalent substituent, and a plurality of X ³ and X ⁴ may be bonded to a connecting portion represented by a solid arc connecting T and U. R is the same or different and represents an oxygen atom or a monovalent substituent, p represents the number of R, and represents a number of 0 to 3). is there.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

（式中、点線の円弧は、ホウ素原子を含む複素環構造の骨格部分の一部と共に環構造が形成されていることを表す。ホウ素原子を含む複素環構造中の点線部分は、少なくとも１対の原子が二重結合で結ばれることを表し、該二重結合が、点線の円弧部分を形成する環構造と共役していてもよい。Ｘ^１及びＸ^２は、同一又は異なって、水素原子又は環構造の置換基となる１価の置換基を表し、点線の円弧部分を形成する環構造にそれぞれ複数個結合していてもよい。Ｕからホウ素原子への矢印は、Ｕ原子がホウ素原子へ配位していることを表す。ＴとＵとを繋ぐ実線の円弧は、ＴとＵとが少なくとも１つの原子を有する連結部分を介して結合していることを表し、該連結部分が環構造を有していてもよく、該連結部分の一部又は全部とＵとが１つ又は複数の環からなる環構造を形成していてもよい。Ｔは、硫黄原子、酸素原子のいずれかを表し、Ｕは、窒素原子、酸素原子、硫黄原子、リン原子のいずれかを表す。Ｘ^３及びＸ^４は、同一又は異なって、水素原子又は１価の置換基を表し、ＴとＵとを繋ぐ実線の円弧で表される連結部分にそれぞれ複数個結合していてもよい。Ｒは、同一又は異なって、酸素原子又は１価の置換基を表す。ｐは、Ｒの数を表し、０〜３の数を表す。）で表される構造を有するものである。 The boron-containing compound 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 a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Alternatively, it represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of each may be bonded to a ring structure forming a dotted arc part.The arrow from U to a boron atom indicates that the U atom is a boron atom The solid arc connecting T and U indicates that T and U are connected via a connecting portion having at least one atom, and the connecting portion is a ring. It may have a structure, and a part or all of the connecting portion and U are A ring structure composed of one or a plurality of rings may be formed, T represents any of a sulfur atom and an oxygen atom, and U represents any of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ³ and X ⁴ may be the same or different and each represents a hydrogen atom or a monovalent substituent, and a plurality of X ³ and X ⁴ may be bonded to a connecting portion represented by a solid arc connecting T and U. R is the same or different and represents an oxygen atom or a monovalent substituent, and p represents the number of R and represents a number of 0 to 3.

The dotted arc in the above formula (1) indicates that a ring structure is formed together with a part of the skeleton portion of the heterocyclic structure containing a boron 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 of the heterocyclic structure containing a boron atom is It is included as a part.
In the above formula (1), the dotted line part in the skeleton part of the heterocyclic structure containing a boron atom represents that at least one pair of atoms is connected by a double bond, and the double bond is conjugated with the ring structure. Represents a good thing. Among the compounds represented by the formula (1), examples in which the double bond is conjugated with the ring structure include structures having the following formulas (2-1) to (2-3). The following (2-1) to (2-3) are for the case where X ^{1 to} X ⁴ are all hydrogen atoms.

In the above formula (1), the arrow from U to the boron atom represents that the U atom is coordinated to the boron atom. Here, being coordinated means that the U atom acts on the boron atom in the same manner as the ligand and has a chemical influence, 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 each of the ring structures forming a dotted arc part is plural. It may be bonded. 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 above formula (1), X ³ and X ⁴ are the same or different and each represents a hydrogen atom or a monovalent substituent, and each of them is bonded to a connecting portion represented by a solid arc connecting T and U. You may do it. Here, the substituent which a connection part has is when the connection part which connects T and U is a ring structure which consists of 1 or a plurality of rings, or when all the connection parts and U are 1 or more When the ring structure which consists of a ring is formed and a connection part does not have chain-like structure parts other than a ring structure, the substituent of the said ring structure is represented. When the linking part is composed of only a chain-like structural part other than the ring structure, the substituent included in the linking part is the chain-like structural part constituting the main chain of the linking part that connects T and U. Represents a monovalent group bonded to. When the connecting part connecting T and U has a ring structure and a chain-like structural part other than the ring structure, a part of the connecting part and U form a ring structure composed of one or more rings, Further, when the linking part also has a chain-like structure part other than the ring structure, it represents a monovalent group bonded to either or both of the substituent of the ring structure and the chain-like structure part.
In the case where X ³ and X ⁴ are hydrogen atoms, in the structure of the boron-containing compound represented by the formula (1), the connecting portion represented by a solid arc connecting T and U has a substituent. In the case where X ³ and / or X ⁴ is a monovalent substituent, the connecting portion represented by a solid arc connecting T and U has at least one substituent. Become.
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.

In the above formula (1), a solid arc connecting T and U represents that T and U are bonded via a connecting portion having at least one atom. In this way, T and U are connected to each other, and a cyclic coordination structure with respect to the boron atom prevents the U atom coordinated to the boron atom from being easily detached. The boron-containing compound of the invention can stably exhibit excellent electrical characteristics.
The connecting portion represented by a solid arc connecting T and U may be composed of one atom or may be composed of a plurality of atoms. Moreover, the connection part may form the ring structure which consists of a 1 or several ring, and the connection part and U may form the ring structure which consists of a 1 or several ring.
When the linking moiety has a ring structure composed of one or a plurality of rings, the linking moiety connecting T and U may be composed only of the ring structure, and atoms that do not form a ring structure with the ring structure It may have a chain-like structure part containing at least one.
When a part of the linking part and U form a ring structure consisting of one or more rings, a part of the linking part and U form a ring structure consisting of one or more rings. Further, this is a case where the linking portion also has a chain-like structure portion containing at least one atom that does not form a ring structure. When all of the linking moieties and U have a ring structure consisting of one or more rings, the linking moiety and U form a ring structure consisting of one or more rings, This is the case where there is no chain-like structure portion containing at least one atom that does not form any other ring structure.

The ring structure composed of a plurality of rings in the connecting portion connecting T and U is one in which a plurality of rings constituting the ring structure are directly bonded, or those bonded via at least one other atom Any of those having a direct bond and a bond via at least one other atom, and those in which a plurality of rings share the atoms constituting the ring may be used. A ring having a structure in which aromatic rings such as naphthalene and anthracene are condensed includes those in which a plurality of rings share the atoms constituting the ring.
When a part or all of the linking part and U form a ring structure consisting of one or more rings, one or more rings are formed in part or all of the linking part, This is a case where a U atom is included as an atom forming one ring. When a part or all of the linking moiety and U form a ring structure composed of a plurality of rings, the number of rings not containing U atoms and the ring containing U atoms and U atoms are included. The form of the bond with the ring that is not present may be any one of the ring structures composed of the plurality of rings.

When the linking part is composed of only a chain-like structure part having no ring structure or a chain-like structure part containing at least one atom that does not form a ring structure other than the ring structure, Examples of the structure of the chain structure portion include a divalent hydrocarbon group and an alkoxyalkyl group that do not have a ring structure having 1 to 8 carbon atoms. Among these, a divalent hydrocarbon group having no ring structure having 2 to 6 carbon atoms is preferable.

Examples of the ring structure in the case where the connecting portion has a ring structure composed of one or a plurality of rings include structures of the following formulas (3-1) to (3-9).

When the linking part consists only of a ring structure consisting of one or more rings, and the ring structure is directly bonded to a T atom or U atom, among the atoms constituting the ring structure, Although the position is not particularly limited, in the case of the benzene ring whose ring structure is represented by (3-1) above, it is preferable that the carbon atom in the ortho position of the carbon atom bonded to the T atom is bonded to the U atom.
When the ring structure is a ring represented by the above (3-2), it is preferable that the 2-position carbon atom is bonded to the T atom and the 2′-position carbon atom is bonded to the U atom.
When the ring structure is a ring represented by the above (3-3) or (3-4), it is preferable that the first carbon atom is bonded to the T atom and the eighth carbon atom is bonded to the U atom.

Examples of the ring structure in the case where a part or all of the linking part and U form a ring structure composed of one or more rings include the following formulas (4-1) to (4-6): A structure is preferred. The following structure is for the case where U is any of a nitrogen atom, an oxygen atom, and a sulfur atom.

When all of the linking moieties and U form a ring structure composed of one or more rings, the position of the atom that binds to the T atom among the atoms constituting the ring structure is not particularly limited, but the ring structure is In the case of the ring represented by (4-1), it is preferable that the carbon atom at the 8-position is bonded to the T atom.
When the ring structure is a ring represented by the above (4-2), it is preferable that the carbon atom at the 10-position is bonded to the T atom.
When the ring structure is a ring represented by the above (4-3), it is preferable that the carbon atom at the 8-position is bonded to the T atom.
When the ring structure is a ring represented by (4-4) above, a ring represented by (4-5), or a ring represented by (4-6), the carbon atom at the 7-position is bonded to the T atom. It is preferable.

The structure of the connecting portion represented by the solid arc connecting T and U includes a structure having no ring structure and a structure having a ring structure as described above.
The structure having a ring structure includes a structure consisting only of a ring structure and a structure having a ring structure and a chain structure.
A structure consisting of only a ring structure is a ring structure in which the linking moiety is composed of one or more rings, or a ring structure in which all of the linking moieties and U are composed of one or more rings.
The structure having a ring structure and a chain structure is a structure having a ring structure in which the linking part is composed of one or more rings and a chain structure part containing at least one atom that does not form a ring structure, or In this structure, a part of the linking moiety and U form a ring structure composed of one or a plurality of rings, and further have a chain-like structure part containing at least one atom that does not form a ring structure.
Among these, as a structure of a connection part, the structure which has a ring structure is preferable. This is because when used as a light emitting material, the kinetic energy inactivation due to molecular motion is less when the ring structure is present than when the ring structure is not present.
More preferably, the structure of the linking moiety is a structure consisting only of a ring structure, that is, the linking moiety is composed of one or more rings, or the linking moiety and U are composed of one or more rings. Any of the ring structures.

In the above formula (1), T represents either a sulfur atom or an oxygen atom, and among these, an oxygen atom is preferable.
U represents any one of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and among these, either a nitrogen atom or an oxygen atom is preferable.
In addition, when both T and U are sulfur atoms or when they are both oxygen atoms, a ring structure in which U is composed of one or a plurality of rings and a connecting portion represented by a solid arc connecting T and U. In the formula (1), p is preferably any one of 0 to 3, and one connecting portion represented by a solid arc connecting T and U and one U or In the case where a ring structure composed of a plurality of rings is not formed, p in formula (1) is preferably any one of 1 to 3.

In the above formula (1), R represents an atom or a substituent bonded to the U atom. R has no bond with the connecting portion represented by the solid arc connecting T and U, and is bonded only to the U atom. p represents the number of R, and represents the number of 0-3. That is, R may not be bonded to the U atom, and when R is bonded to the U atom, the number is any one of 1 to 3. When two or three Rs are bonded to a U atom, the plurality of Rs may be the same or different.

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. X ³ and X ⁴ are the same or different and each represents a monovalent substituent bonded to a hydrogen atom or a connecting portion represented by a solid arc connecting T and U. R represents an oxygen atom or a monovalent substituent.
As monovalent substituents for X ¹ , X ² , X ³ , X ⁴ and R, a halogen atom of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl chloride group, a methyl bromide group or a methyl iodide group Haloalkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. 1 -4 linear or branched alkyl groups; C5-C7 cyclic alkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, 1 carbon number such as isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc. A linear or branched alkoxy group of ~ 8; hydroxyl group; thiol group; epoxy group; nitro group; azo group; allyl group; cyano group; amino group; methylamino group, ethylamino group, dimethylamino group, diethylamino group Mono- or dialkylamino groups having an alkyl group of 1 to 4 carbon atoms such as a group; amino groups such as diphenylamino group and carbazolyl group; acyl groups such as acetyl group, propionyl group and butyryl group; vinyl group and 1-propenyl group An alkynyl group having 2 to 8 carbon atoms such as 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 and phenylacetylin; vinyloxy group and allyloxy group Alkenyloxy groups such as ethynyloxy groups, phenylacetyloxy groups and the like; Aryloxy groups such as an enoxy group, a naphthoxy group, a biphenyloxy group, and a pyrenyloxy group; a perfluoro group such as a trifluoromethyl group, a trifluoromethoxy group, and a pentafluoroethoxy group; and a long-chain perfluoro group; a diphenylboryl group; Boryl groups such as dimesitylboryl group, bis (perfluorophenyl) boryl group and diboronic acid ester group; carbonyl groups such as acetyl group and benzoyl group; carbonyloxy groups such as acetoxy group and benzoyloxy group; methoxycarbonyl group and ethoxycarbonyl group , Alkoxycarbonyl groups such as phenoxycarbonyl group; sulfinyl groups such as methylsulfinyl group and phenylsulfinyl group; trimethylsilyl group, triisopropylsilyl group, dimethyl-tert-butylsilyl group, trimethoxy Silyl groups such as ryl group and triphenylsilyl group; phenyl group, 2,6-xylyl group, mesityl group, duryl group, biphenyl group, terphenyl group which may be substituted with halogen atom, alkyl group, alkoxy group or the like Aryl groups such as naphthyl group, anthryl group, pyrenyl group, toluyl group, anisyl group, fluorophenyl group, diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, phenanthrenyl group; oligoaryl group; thienyl group, furyl group , Silacyclopentadienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl group, quinolyl group, quinoxaloyl group, phenanthrolyl group, benzothienyl group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl group , Pyrrolyl group, benzoxazolyl group, pyrimidyl group, imidazolyl group, etc .; oligo heterocyclic group; carboxyl group; carboxylate ester; epoxy group; isocyano group; cyanate group; isocyanate group; thiocyanate group; Carbamoyl group; N, N-dicarbcarbamoyl group such as N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group; formyl group; nitroso group; formyloxy group; stannyl group; phosphino group; silyloxy group; Oxy group; alkylsulfonyloxy group; arylthio group; arylalkyl group; arylalkenyl group; arylalkynyl group; arylalkoxy group; arylalkylthio group;

Among these, as a monovalent substituent of X ¹ , X ² , X ³ , X ⁴ and R, a halogen atom of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl chloride group or a methyl bromide group Haloalkyl groups such as methyl iodide group, fluoromethyl group, difluoromethyl group, trifluoromethyl group; carboxyl group, hydroxyl group, thiol group, epoxy group, isocyanate group, amino group, azo group, acyl group, allyl group, Reactive groups such as nitro group, alkoxycarbonyl group, formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy group; A linear or branched chain having 1 to 4 carbon atoms substituted with a linear or branched alkyl group or the reactive group An alkyl group; a linear or branched alkoxy group having 1 to 8 carbon atoms or a linear or branched alkoxy group having 1 to 8 carbon atoms substituted by the reactive group; an aryl group or the reactive group An aryl group substituted with an oligoaryl group or an oligoaryl group substituted with the reactive group; a monovalent heterocyclic group or a monovalent heterocyclic group substituted with the reactive group; A monovalent oligoheterocyclic group substituted with a cyclic group or the reactive group; an alkylthio group; an aryloxy group; an arylthio group; an arylalkyl group; an arylalkoxy group; an arylalkylthio group; an alkenyl group or a substituted group with the reactive group An alkynyl group or an alkynyl group substituted with the reactive group is preferred. More preferably, a hydrogen atom, bromine atom, iodine atom, boryl group, alkynyl group, alkenyl group, formyl group, stannyl group, phosphino group, aryl group substituted with the reactive group, substituted with the reactive group Oligoaryl group, monovalent heterocyclic group substituted with the reactive group, monovalent oligo heterocyclic group substituted with the reactive group, alkenyl group, or alkenyl group substituted with the reactive group, alkynyl Or an alkynyl group substituted with the reactive group.
When the boron-containing compound of the present invention is the above formula (1) and X ¹ and / or X ² is a monovalent substituent, the bonding position and the number of X ¹ and / or X ² with respect to the ring structure are as follows: Although not particularly limited, the number of X ¹ and X ² is preferably 1 to 5, respectively. More preferably, it is 1-4.
The connecting portion connecting the T and U has a ring structure, when X ³ and / or X ⁴ is a monovalent substituent bonded to the ring structure, X ³ and / or X ⁴ with respect to the ring structure The bonding position and the number of bonds are not particularly limited, but the number of X ³ and X ⁴ is preferably 1 to 5, respectively. More preferably, it is 1-4.

In the above formula (1), any one of X ^{1 to} X ⁴ is a monovalent substituent, the remaining three are hydrogen atoms, X ¹ and X ² are monovalent substituents, ³ and X ⁴ are hydrogen atoms, X ² and X ⁴ are monovalent substituents, X ¹ and X ³ are hydrogen atoms, and X ^{1 to} X ⁴ are all hydrogen atoms , X ^{1 to} X ⁴ are all preferably monovalent substituents. More preferably, X ¹ and X ² are monovalent substituents, X ³ and X ⁴ are hydrogen atoms, X ^{1 to} X ⁴ are all hydrogen atoms, X ^{1 to} X ⁴ All are monovalent substituents.

In the present invention, it is also preferable that at least one of X ¹ , X ² , X ³ , X ⁴ and R in the above formula (1) is a substituent having a reactive group. One of the forms. In the case where X ¹ , X ² , X ³ , X ⁴ and R are substituents having a reactive group among those described above, examples of such substituents include a halogen atom, a carboxyl group, and a 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, A reactive group such as an arylsulfonyloxy group or an alkylsulfonyloxy group; a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the reactive group; a carbon number of 1 substituted with the reactive group -8 linear or branched alkoxy groups; aryl groups substituted with the reactive groups; oligoaryl groups substituted with the reactive groups; substituted with the reactive groups A monovalent heterocyclic group substituted with the reactive group; an alkenyl group substituted with the alkenyl group or the reactive group; an alkynyl group substituted with the reactive group; Alkynyl groups are preferred. 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 at least one of the above X ¹ , X ² , X ³ , X ⁴ and R is a substituent having a reactive group, (I) among X ¹ , X ² , X ³ , X ⁴ and R At least one is a substituent having a reactive group capable of polymerizing alone, or (II) ^{two of} X ¹ , X ² , X ³ , X ⁴ and R are reactive groups, These reactive groups are supposed to be able to react with each other, and one type of boron-containing compound is made to be a combination of reactive groups capable of polycondensation alone, or (III) represented by the formula (1) Or a combination of reactive groups such that these boron-containing compounds can be copolymerized, or (IV) represented by formula (1) One or more boron-containing compounds and at least one reactive group By the other compounds are made to be those having a combination of reactive groups such as copolymerizable, it can be suitably used as a raw material of the polymer.
A polymer obtained from such a boron-containing compound can be suitably used as a polymer n-type organic semiconductor suitable for a coating process.

In the above formula (1), the ring structure formed by the dotted arc and a part of the skeleton part of the heterocyclic structure containing a boron atom is not particularly limited as long as it is a cyclic structure. Examples of the ring to which ¹ is bonded and the ring to which X ² is bonded include, for example, a benzene ring, a thiophene ring, a benzothiophene ring, a thiazole ring, an oxazole ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, and a pyrrole. Ring, imidazole ring, pyrazole ring, pyridine ring, pyridazine ring, pyrazine ring, pyrimidine ring, indole ring, isoindole ring, quinoline ring, isoquinoline ring, and phenanthridine ring, each of which is represented by the following formula (5- 1) to (5-21). Among these, a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, a pyridine ring, and a quinoline ring are preferable.

Examples of the preferred structure of the boron-containing compound of the present invention include the following (6-1) to (6-17).

Since the boron-containing compound of the present invention has a low LUMO energy level, it can be suitably used as an n-type semiconductor material or an organic EL device material. 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 an n-type semiconductor material or an organic EL element material, the 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.
The LUMO energy level can be obtained as follows.
<LUMO energy levels>
A p-doped silicon substrate (manufactured by Furuuchi Chemical Co., Ltd.) is cut into 25 mm square, and ultrasonically washed in acetone and isopropyl alcohol for 10 minutes, respectively, and then subjected to UV ozone treatment for 20 minutes. Then, this board | substrate is fixed to the board | substrate holder of the vacuum evaporation apparatus (made by ULVAC) connected with the glove box of argon atmosphere. A sample to be measured is put in a quartz crucible, and the pressure is reduced to about 1 × 10 ⁻³ Pa. For the created measurement sample, an ionization potential is measured using an ultraviolet photoelectron spectrometer (manufactured by Kobelco Kaken Co., Ltd.), and the measured value is set as the energy level of the highest occupied orbit (HOMO) of the sample.
At the same time, the absorption spectrum of another sample thin film prepared in the same manner as described above is measured using an ultraviolet-visible spectrophotometer (product name “Agilent 8453”, manufactured by Agilent Technologies). A long wavelength side absorption edge λ (unit: nm) of an absorption peak is read from the obtained spectrum, and a HOMO-LUMO gap (B.G.) is obtained by the following 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. Obtain the LUMO energy level.

One of the preferred embodiments of the present invention is that the boron-containing compound of the present invention has a structure represented by the above formula (1), and the emission quantum yield is 20 to 100%. It is. When the emission quantum yield of the boron-containing compound is in such a range, sufficiently stable light emission can be obtained when used as a light-emitting layer in an organic EL device, a HOILED device, or the like. More preferably, it is 30 to 100% as an emission quantum yield, More preferably, it is 40 to 100%.
The emission quantum yield can be determined as follows.
<Luminescent quantum yield>
For the boron-containing compound, several types of dichloromethane solutions having different concentrations are prepared, and the absorbance of each solution is measured using an ultraviolet-visible spectrophotometer (product name “Agilent 8453”, manufactured by Agilent Technologies). Further, the fluorescence spectrum of each solution is measured by the following method to determine the fluorescence intensity (wave number integral value). From the obtained absorbance and fluorescence intensity, a graph is prepared in which the horizontal axis represents absorbance and the vertical axis represents fluorescence intensity. Further, as a standard substance, quinine sulfate 0.1 M sulfuric acid solution is measured in the same manner, and respective graphs are 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 is determined by the following mathematical formula (3), where n _R and quinine sulfate (document values) are Y _R. For n _S , n _R , and Y _R , values of n _S = 1.4242, n _R = 1.333, and Y _R = 0.54 are used as literature values.

<Fluorescence spectrum>
A dilute dichloromethane solution of a boron-containing compound is prepared, and a fluorescence spectrum is 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

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.

The present invention also provides the following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Alternatively, it represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of each may be bonded to a ring structure forming a dotted arc part.The arrow from U to a boron atom indicates that the U atom is a boron atom The solid arc connecting T and U indicates that T and U are connected via a connecting portion having at least one atom, and the connecting portion is a ring. It may have a structure, and a part or all of the connecting portion and U are A ring structure composed of one or a plurality of rings may be formed, T represents any of a sulfur atom and an oxygen atom, and U represents any of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ³ and X ⁴ may be the same or different and each represents a hydrogen atom or a monovalent substituent, and a plurality of X ³ and X ⁴ may be bonded to a connecting portion represented by a solid arc connecting T and U. R is the same or different and represents an oxygen atom or a monovalent substituent, p represents the number of R, and represents a number of 0 to 3). ,
The production method comprises the following formula (2):

(In the formula, a dotted arc represents that a ring structure is formed together with a part of a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Or a monovalent substituent as a substituent of the ring structure, and a plurality of each may be bonded to the ring structure forming the dotted arc part, Q is a compound represented by the formula (3) And a compound represented by the following formula (3):

(In the formula, X represents a hydrogen atom or a metal atom. A solid line arc connecting T and U represents that T and U are bonded via a connecting portion having at least one atom; The linking part may have a ring structure, and a part or all of the linking part and U may form a ring structure composed of one or more rings, and T is a sulfur atom or Represents an oxygen atom, U represents a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X ³ and X ⁴ are the same or different and represent a hydrogen atom or a monovalent substituent; A plurality of connecting portions each represented by a solid arc connecting U may be bonded to each other, R may be the same or different and each represents an oxygen atom or a monovalent substituent, and p represents the number of Rs. And represents a number of 0 to 3)), and a step of reacting with the compound represented by It is also a method of manufacturing that the boron-containing compound.

The method for producing a boron-containing compound of the present invention includes other steps as long as it includes a step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3). May be. Further, each of the compound represented by the above formula (2) and the compound represented by the above formula (3) may be a single compound or two or more compounds.
The compound represented by the above formula (2) can be produced by a method similar to the method described in Synthesis Examples described later.

The dotted arc in the above formula (2) means that the compound has at least two ring structures in the structure. The formula (2) ^X 1, ^{X 2} and specific examples and preferred ones of the ring structure in is the same as ^X 1, ^{X 2} and ring structures in the above formula (1).
Q in the above formula (2) is a monovalent group that is eliminated by the reaction with the compound represented by the formula (3). Examples of such a monovalent group include a halogen atom, a hydroxyl group, and an alkoxy group. Among these, Q is preferably a halogen atom. More preferably, they are a fluorine atom, a chlorine atom, and a bromine atom.

The structure of the connecting portion connecting T and U represented by the solid arc connecting T and U in the above formula (3), the connecting portion or the ring structure in which the connecting portion and U are one or more rings Specific examples and preferred examples of the ring structure in the case of forming are the same as those in the above formula (1). Specific examples and preferred examples of T, U, X ³ , X ⁴ , R and p in the above formula (3) are the same as those in the above formula (1).
X in the formula (3) is a leaving group that is eliminated by the reaction with the compound represented by the formula (2), and represents a hydrogen atom or a metal atom. Examples of the metal atom include lithium, aluminum, and zinc. Among these, X is preferably a hydrogen atom.

When the compound represented by the formula (2) and the compound represented by the formula (3) are reacted, the compound represented by the formula (3) is represented with respect to 1 mol of the compound represented by the formula (2). It is preferable to use 1 mol to 5 mol of the compound. More preferably, it is 1 mol-3 mol, and even if it considers from an industrial surface, it is preferable to use especially 1 mol-1.5 mol.

The solvent used in the step of reacting the compound represented by the above formula (2) and the compound represented by the above formula (3) 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; Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone; ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosol) ), Glycol ethers (cellosolves) such as ethylene glycol monoethyl ether acetate (cellosolve acetate); dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2 -Halogenated aliphatic hydrocarbons such as tetrachloroethane, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as n-hexane; benzene, toluene, xylene, One kind or two or more kinds of aromatic hydrocarbons such as mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene can be used. 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 formula (2) with the compound represented by the formula (3), 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 it is 1 mol-10 mol as a usage-amount of a reaction accelerator with respect to 1 mol of compounds represented by the said Formula (2). 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 (2) with the compound represented by the formula (3) 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 (2) with the compound represented by the formula (3) 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 method for producing a boron-containing compound of the present invention is represented by the formula (1) obtained after the step of reacting the compound represented by the formula (2) with the compound represented by the formula (3). A step of purifying the boron-containing compound to be produced may be included. The purification method is not particularly limited, and a suitable method can be appropriately selected from methods such as extraction, filtration, column chromatography, recrystallization, and sublimation. Moreover, any one of these purification methods may be used, and two or more may be used.

The boron-containing compound of the present invention can be suitably used as a material for n-type semiconductors and organic EL devices. 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 of the present invention can be suitably used as a material for an n-type semiconductor or an organic EL element. Thus, it is also one aspect of the present invention that the boron-containing compound of the present invention is used for forming a light emitting device. Such a light-emitting device formed using the boron-containing compound of the present invention is also one aspect of the present invention.
Further, among the boron-containing compounds 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, and therefore, among light-emitting devices, It is preferably used for forming a light emitting layer of an organic EL element or a HOILED element.

The boron-containing compound of the present invention has the above-described configuration, has a low LUMO energy level, is excellent in properties as a functional electronic device material, and further has stability due to its structure. Therefore, it can be suitably used as a material for n-type organic semiconductors and organic EL elements, especially HOILED elements.

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, ¹ H-NMR was 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.

Example 1
8-Quinolinol (302 mg, 2.1 mmol) was added to a 100 ml eggplant flask and purged with nitrogen. Triethylamine (493 mg, 3.8 mmol) was added thereto, 15 ml of toluene was further added, and the atmosphere was replaced with nitrogen, followed by stirring at room temperature for 5 minutes. A solution prepared by dissolving 5-bromodibenzoborol in 5 ml of toluene was added thereto. This was heated and stirred at 110 ° C. for 24 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The organic layer was dried using sodium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain the desired product. This reaction is a reaction of the following formula (7).
The physical properties of the obtained target product are as follows.
¹ H-NMR (CDCl ₃ ): δ 7.05-7.13 (m, 4H), 7.20 (d, 1H), 7.28-7.33 (m, 3H), 7.45-7. 48 (m, 1H), 7.68-7.74 (m, 3H), 8.01 (d, 1H), 8.40 (d, 1H)

Synthesis Example 1-1
To a 300 ml three-necked flask, 115 ml of dehydrated tetrahydrofuran was added and purged with nitrogen. To this, 8.6 ml of a 1.63 M normal butyl lithium hexane solution was added and cooled to -78 ° C. Over a period of 30 minutes, a solution prepared by dissolving 2,2′-dibromothiophene (2270 mg, 7.0 mmol) in 23 ml of dehydrated tetrahydrofuran was added dropwise. The mixture was stirred at −78 ° C. for 1 hour. To this, a solution prepared by dissolving dichlorodimethylsilane (994 mg, 7.7 mmol) in 23 ml of dehydrated tetrahydrane was added dropwise at −78 ° C. The temperature was gradually raised from −78 ° C. to room temperature and stirred overnight. Quench with saturated aqueous sodium chloride and extract three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography using hexane as a mobile phase to obtain the desired product. This reaction is a reaction of the following formula (8).
The physical properties of the obtained target product are as follows.
¹ H-NMR (CDCl ₃ ): δ0.42 (s, 6H), 7.08 (d, 2H), 7.21 (d, 2H)

Synthesis Example 1-2
To a 100 ml three-necked flask, 35 ml of dehydrated N, N′-dimethylformamide and dithienosilol (930 mg, 4.2 mmol) were added, and the atmosphere was replaced with nitrogen. NBS (1625 mg, 9.1 mmol) was added at room temperature. After stirring at room temperature for 2 hours, water was added and extracted three times with ethyl acetate. The organic layer was washed with water and then dried over magnesium sulfate. After filtration, the solvent was distilled off to obtain a crude product. The obtained crude product was purified by silica gel column chromatography using hexane as a mobile phase to obtain the desired product. This reaction is a reaction of the following formula (9).
The physical properties of the obtained target product are as follows.
¹ H-NMR (CDCl ₃ ): δ0.40 (s, 6H), 7.02 (s, 2H)

Example 2
Dibromodithienosilol (1140 mg, 3 mmol) was added to a 10 ml Schlenk flask and purged with nitrogen. To this was added 3 ml of boron tribromide, and the mixture was heated and stirred at 50 ° C. for 48 hours. An alkali trap was connected here, and after flowing nitrogen for 12 hours, hexane was added to the reaction vessel, and the solid was filtered. Further, it was washed with hexane, and the obtained intermediate in the above formula was used in the next reaction without further purification.
To a 20 ml Schlenk flask, 8-quinolinol (160 mg, 1.1 mmol) and 8 ml of dehydrated toluene were added and purged with nitrogen. Triethylamine (202 mg, 2.0 mmol) was added thereto, and the mixture was stirred at room temperature for 10 minutes. To this, 410 mg of the intermediate in the above formula obtained earlier was added, and the mixture was heated and stirred at 70 ° C. for 12 hours. After completion of the reaction, water was added and extracted three times with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained solid was washed with methanol to obtain the desired product. This reaction is a reaction of the following formula (10).
The physical property values are as follows.
¹ H-NMR (CDCl 3): δ 6.99 (s, 2H), 7.26-7.51 (m, 3H), 7.64 (t, 1H), 7.88-7.90 (m, 1H ), 8.37-8.39 (m, 1H)

Claims (5)

A boron-containing compound having a heterocyclic structure containing a boron atom,
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 a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Alternatively, it represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of each may be bonded to a ring structure forming a dotted arc part.The arrow from U to a boron atom indicates that the U atom is a boron atom The solid arc connecting T and U indicates that T and U are connected via a connecting portion having at least one atom, and the connecting portion is a ring. It may have a structure, and a part or all of the connecting portion and U are A ring structure composed of one or a plurality of rings may be formed, T represents any of a sulfur atom and an oxygen atom, and U represents any of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ³ and X ⁴ may be the same or different and each represents a hydrogen atom or a monovalent substituent, and a plurality of X ³ and X ⁴ may be bonded to a connecting portion represented by a solid arc connecting T and U. R is the same or different and represents an oxygen atom or a monovalent substituent, and p represents the number of R, and represents a number of 0 to 3.). The boron-containing compound according to claim 1, wherein the boron-containing compound has an emission quantum yield of 20 to 100%. ^{3. The} boron-containing compound according to claim ¹ , wherein at least one of X ¹ , X ² , X ³ , X ⁴ and R in the formula (1) is a substituent having a reactive group. The boron-containing compound as described. The said boron containing compound is used for light emitting device formation, The boron containing compound in any one of Claims 1-3 characterized by the above-mentioned. Following formula (1);

(In the formula, a dotted arc represents that a ring structure is formed together with a part of a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Alternatively, it represents a monovalent substituent serving as a substituent of the ring structure, and a plurality of each may be bonded to a ring structure forming a dotted arc part.The arrow from U to a boron atom indicates that the U atom is a boron atom The solid arc connecting T and U indicates that T and U are connected via a connecting portion having at least one atom, and the connecting portion is a ring. It may have a structure, and a part or all of the connecting portion and U are A ring structure composed of one or a plurality of rings may be formed, T represents any of a sulfur atom and an oxygen atom, and U represents any of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ³ and X ⁴ may be the same or different and each represents a hydrogen atom or a monovalent substituent, and a plurality of X ³ and X ⁴ may be bonded to a connecting portion represented by a solid arc connecting T and U. R is the same or different and represents an oxygen atom or a monovalent substituent, p represents the number of R, and represents a number of 0 to 3). ,
The production method comprises the following formula (2):

(In the formula, a dotted arc represents that a ring structure is formed together with a part of a skeleton part of a heterocyclic structure containing a boron atom. At least one pair of dotted parts in a heterocyclic structure containing a boron atom is present. And X ¹ and X ² may be the same or different and represent a hydrogen atom, which may be conjugated with a ring structure that forms a dotted arc portion. Or a monovalent substituent as a substituent of the ring structure, and a plurality of each may be bonded to the ring structure forming the dotted arc part, Q is a compound represented by the formula (3) And a compound represented by the following formula (3):

(In the formula, X represents a hydrogen atom or a metal atom. A solid line arc connecting T and U represents that T and U are bonded via a connecting portion having at least one atom; The linking part may have a ring structure, and a part or all of the linking part and U may form a ring structure composed of one or more rings, and T is a sulfur atom or Represents an oxygen atom, U represents a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X ³ and X ⁴ are the same or different and represent a hydrogen atom or a monovalent substituent; A plurality of connecting portions each represented by a solid arc connecting U may be bonded to each other, R may be the same or different and each represents an oxygen atom or a monovalent substituent, and p represents the number of Rs. And represents a number of 0 to 3)), and a step of reacting with the compound represented by Method of manufacturing that the boron-containing compound.