WO2011099331A1 - Composé contenant du bore et son procédé de préparation - Google Patents

Composé contenant du bore et son procédé de préparation Download PDF

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WO2011099331A1
WO2011099331A1 PCT/JP2011/050722 JP2011050722W WO2011099331A1 WO 2011099331 A1 WO2011099331 A1 WO 2011099331A1 JP 2011050722 W JP2011050722 W JP 2011050722W WO 2011099331 A1 WO2011099331 A1 WO 2011099331A1
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group
boron
atom
formula
mmol
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Japanese (ja)
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正浩 村上
直樹 石田
大作 守屋
剛 呉屋
克行 森井
宗弘 長谷川
洋一 有元
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国立大学法人京都大学
株式会社日本触媒
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values

Definitions

  • 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.
  • a functional electronic element material such as a light emitting device such as an organic EL element or a material of an organic semiconductor
  • 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.
  • 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.
  • organic EL elements have various excellent characteristics as displays, development of materials capable of realizing further higher performance has been actively promoted.
  • HOILED Hybrid Organic-Inorganic Light-Emitting Diode
  • the HOILED element has an advantage that it has higher resistance to oxygen and water than the organic EL element by being hybridized.
  • 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.
  • 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.
  • 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).
  • an organic boron ⁇ -electron compound having a specific structure is used as an electron transporting material (see, for example, Patent Document 2). It has actually been shown that the LUMO energy level of the compound is low (see Non-Patent Document 1, for example).
  • 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).
  • 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).
  • organic EL element materials that are organic boron-containing compounds having a specific structure having 3 to 15 boron atoms in the molecule (see, for example, Patent Document 5), and organic boron-containing compounds having a specific structure.
  • An organic EL element material (for example, see Patent Document 6) is disclosed.
  • HOILED element fluorene and polyfluorene derivatives in which various derivatives are known in the field of material chemistry have been studied.
  • 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
  • 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.
  • Patent Document 7 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)
  • Organoboron compounds are derived 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).
  • HOMO highest occupied orbital
  • LUMO lowest vacant orbital
  • 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.
  • the performance as a functional electronic device is improved.
  • light emission in a general configuration of the polymer organic EL that is, a configuration in which an anode is formed from a transparent electrode, a hole (hole) transport layer, a light emitting and electron transport layer, a cathode formed from Ca, Ba, or the like. 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 similarly improved.
  • HOILED elements the LUMO of fluorene and polyfluorene derivatives that have been studied in the past is high, and is actually unsuitable for HOILED elements, and stable light emission cannot be obtained.
  • LUMO is low, and further development of an excellent material as a light emitting material is expected.
  • a 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 a compound has great technical significance when the compound itself is used as an element material in the field of an organic EL element, an N-type semiconductor, a HOILED element, or when a polymer prepared from the compound is used. There is.
  • organic boron compounds have many structures in which three aryl groups are bonded to a boron atom because haloboron compounds such as fluorodimesitylborane and 5-bromodibenzoborol, which are precursors, are stable. This is because the substituent on the boron has a bulky structure in order to obtain the properties.
  • 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.
  • 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.
  • a pseudo-fluorene compound group having a low LUMO instead of fluorene and polyfluorene, which have been studied as materials for HOILED elements, there is a possibility that the practical application of HOILED elements will 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 novel boron-containing compounds and new methods for producing various boron-containing compounds.
  • nitrogen is added to the boron atom. It was noticed that the atoms should have a coordinated structure.
  • 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.
  • 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 without using an expensive palladium catalyst can be produced. .
  • 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.
  • a boron-containing compound that can be particularly suitably used as a light-emitting material constituting a light-emitting layer of a HOILED element, as a light-emitting material constituting a light-emitting layer of an EL element or the like.
  • 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
  • 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).
  • 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).
  • 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);
  • 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 to the 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):
  • 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 to the 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, but itself is a light emitter. It is used as
  • 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.
  • 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.
  • examples in which the double bond is conjugated with the ring structure include those having the structures of the following formulas (2-1) to (2-4).
  • the arrow from the nitrogen atom to the boron atom represents that the nitrogen atom is coordinated to the boron atom.
  • being coordinated means that the nitrogen 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.
  • 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.
  • X 1 and X 2 are hydrogen atoms
  • two ring structures having X 1 and X 2 do not have a substituent.
  • X 1 and / or X 2 is a monovalent substituent
  • either one of the two ring structures or both have a substituent.
  • the number of substituents in one ring structure may be one, or two or more.
  • 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.
  • 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 3.0 eV to 5.2 eV, for example. 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 LUMO energy level is more preferably 3.2 eV to 5.1 eV, and still more preferably 3.4 eV to 5.0 eV. Particularly preferred 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.
  • 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
  • aryl group examples 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.
  • heterocyclic group examples include pyrrolyl group, pyridyl group, quinolyl group, piperidinyl group, piperidino group, furyl group, thienyl group and the like. Among these, a pyridyl group and a thienyl group are preferable.
  • 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.
  • alkyl group examples include a linear or branched hydrocarbon group having 1 to 30 carbon atoms and an alicyclic hydrocarbon group having 3 to 30 carbon atoms. That is, in the light-emitting 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.
  • 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.
  • branched hydrocarbon group having 1 to 30 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group and the like.
  • 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, A haloalkyl group such as a fluoromethyl group; a linear or branched chain having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 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; Carbam
  • the monovalent substituent in R 1 and R 2 includes 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 ethyl group, isopropyl group, octyl group, fluorine atom, bromine atom, vinyl group, ethynyl group, diphenylamino group, diphenylaminophenyl group and trifluoromethyl group.
  • 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.
  • 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.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom or a monovalent substituent that serves 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.
  • 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 Groups, formyl groups, cyano groups, silyl groups, stannyl groups, boryl groups, phosphino groups, silyloxy groups, arylsulfonyloxy groups, alkylsulfonyloxy groups, etc .; linear or branched chains 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
  • a monovalent heterocyclic group substituted by an amino group such as a substituted oligoaryl group, a diphenylamino group, a monovalent heterocyclic group such as a group represented by the following formula (3-10), or the reactive group ,
  • 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.
  • substituents include halogen atoms, carboxyl groups, hydroxyl groups, thiol groups, epoxy groups, isocyanate groups.
  • 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 group 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
  • 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.
  • 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.
  • the ring to which 1 is bonded include 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, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyridazine.
  • a ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, and an isoquinoline ring which are represented by the following formulas (4-1) to (4-17), respectively.
  • 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).
  • 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.
  • the bonding position and the number of X 1 and / or X 2 with respect to the ring structure are as follows: There is no particular limitation.
  • X 1 at least two monovalent substituents are bonded to the ring structure, and one of the monovalent substituents is a boryl group which may have a substituent
  • the monovalent Another embodiment of the present invention is a pyridyl group which may have a substituent, wherein the nitrogen atom of the pyridyl group is coordinated to the boron atom of the boryl group.
  • 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.
  • the boron-containing compound in the present invention has a structure represented by the above formula (1), and the emission quantum yield is 20 to 100%. It is.
  • 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 element or a HOILED element. It becomes.
  • the luminescence quantum yield is more preferably 30 to 100%, and still more preferably 40 to 100%. Particularly preferred is 50 to 100%, and most preferred is 60 to 100%.
  • 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 ⁇ - ⁇ 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.
  • 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);
  • 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 to the 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
  • 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 a substituent include structures represented by the following 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.
  • 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.
  • 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 serving as a substituent of the ring structure, and may represent that a plurality of bonds may be bonded to the ring structure forming the dotted arc portion in the formula (6-2). ing.
  • 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 .
  • atoms that can form double bonds are respectively represented by carbon atoms, 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.
  • 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).
  • Y 1 is a 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 .; linear 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
  • 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 the 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.
  • the monovalent substituent include those similar to X 1 and X 2 in the above formula (1), and among these, a group represented by the above formula (3-10), a naphthyl group, phenyl Particularly preferred is a group.
  • 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
  • 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);
  • 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 to the 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 may be the same or different and each represents a hydrogen atom or a monovalent substituent.)
  • 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.
  • 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.
  • the double bond portion composed of atoms bonded to the ring structure forming the dotted arc portion in the above formula (1) is largely.
  • specific examples include the following 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 that of Formula (1).
  • the dotted arc is the same as the formula (1).
  • 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).
  • 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 the above formulas (1′-1) and (1′-4) are used.
  • 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.
  • the dotted circular arc represents that a ring structure is formed together with a part of the skeleton part connecting the boron atom and the nitrogen atom, as in the formula (1).
  • the ring structure formed by the dotted arc and a part of the skeleton part that connects 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 ring as the ring to which X 1 in Formula (1) is bonded.
  • examples of the ring to which the group having Y 4 is bonded include the same rings as the ring to which X 2 in the formula (1) is bonded.
  • the dotted circular arc in contact with a part of the skeleton part connecting the boron atom and the nitrogen atom is the same 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.
  • 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.
  • the boron-containing compound represented by the above formula (1′-4) has at least four ring structures in the structure, 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.
  • the ring structure formed by a part is not particularly limited as long as it is a cyclic structure, but as a ring to which a group containing a double bond portion formed by Z 5 and Z 6 is bonded, in formula (1), Examples are the same as the ring to which X 1 is bonded. 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 rings as the ring to which X 2 in Formula (1) is bonded.
  • 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);
  • 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
  • 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).
  • 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 above production method may include other steps as long as it includes a step of reacting the compound represented by the above formula (I) with the compound represented by the above formula (II).
  • 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).
  • the compound represented by the above formula (I) 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 to 7 mol, and it is particularly preferable to use 1 mol to 3 mol from the industrial viewpoint.
  • 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 cellos
  • halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane
  • aromatic hydrocarbons such as benzene and toluene
  • 1 type (s) or 2 or more types can be used for a solvent.
  • reaction accelerator 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.
  • 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.
  • the amount of the reaction accelerator used is preferably 1 mol to 10 mol with respect to 1 mol of the compound represented by the formula (I). More preferably, it is 1 mol to 5 mol, and particularly preferably 1 mol to 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 above formula (I) with the compound represented by the above 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):
  • 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.
  • 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.
  • 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).
  • the metal element-containing compound represented by) is preferably used in an amount of 0.33 mol to 5 mol, depending on the valence of the metal element. More preferably, it is from 0.67 mol to 4 mol, and particularly preferably from 1 mol to 3 mol from the viewpoint of industrial and practical use.
  • 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).
  • 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.
  • 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 using 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.
  • halogen atom in the metal halide examples include a chlorine atom, a bromine atom, and an iodine atom
  • metal element in the metal halide examples include zinc and aluminum.
  • zinc chloride and zinc bromide are preferable as the metal halide.
  • 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.
  • a step of reacting the compound represented by the above formula (I) with the compound represented by the above formula (II) is performed.
  • 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 depending on the purpose. be able to.
  • Boron-containing compounds with various substituents bonded to the structure 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.
  • reaction conditions for the coupling reaction reaction conditions under which each coupling reaction is usually performed as described later can be appropriately employed.
  • 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 (16).
  • 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 (16) are collectively referred to as the boron-containing polymer of the present invention. That's it.
  • 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 to the 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 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);
  • 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 a part of the main chain of the polymer.
  • X 1 ′ and X 2 in the formula (1) are polycondensed to form a boron-containing polymer, X 1 ′ and X 2 in the formula (7) are formed.
  • X 1 ′, X 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.
  • R 1 'and R 2' in the, R 1 and R 2, respectively formula (1) are preferably the same groups.
  • R 1 ′ and R 2 ′ may be a linear or branched hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 30 carbon atoms. Further preferred.
  • 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.
  • examples of the structure obtained by polycondensation include the structures of the following formulas (8-1) to (8-6). .
  • the structures of formula (8-1) and formula (8-6) are preferable.
  • More preferred is the structure of formula (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.
  • 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
  • X 1 ′ and X 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.
  • the residue may or may not remain in the polymer.
  • 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.
  • 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.
  • a substituent having a reactive group that forms a combination of the reactive groups capable of polycondensation undergoes a polycondensation reaction and a residue remains in the polymer
  • a substituent having a carboxyl group and a hydroxy group The combination with the substituent which has group is mentioned.
  • the residue remaining in the polymer is a —CH 2 (CO) —O—CH 2 CH 2 — group.
  • 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. -Underlying.
  • specific examples of the case where the combination of the 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, and a halogen atom and a halogen atom. It is done.
  • a structure obtained by polymerizing X 2 is a structure represented by the following formula (9).
  • 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.
  • 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, halogen atom and the like.
  • 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.
  • an alkenyl group, an epoxy group, and a 3,5-dibromophenyl group are preferable.
  • the polycondensable group may be a substituent having a reactive group capable of polycondensation in its structure.
  • the group which homopolymerizes should just be a substituent which has the reactive group which can superpose
  • substituents include linear or branched alkyl groups having 1 to 4 carbon atoms, cyclic alkyl groups having 3 to 7 carbon atoms, linear or branched alkoxy groups having 1 to 8 carbon atoms, and aryl groups.
  • 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 is substituted with a reactive group capable of polycondensation or a reactive group capable of being polymerized alone.
  • a styryl group and a 3,5-dibromophenyl group are preferable.
  • 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);
  • 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 the other monomer represented by (1), which is a substituent 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, tri
  • Examples of A include the structures of the following formulas (11-1) to (11-4) in addition to those described above.
  • 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
  • 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
  • Q3, Q4 and Q5 are the same or different and represent a hydrogen atom, an alkyl group,
  • 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), terphenyl-diyl groups represented by the following formulas (12-11) to (12-12), stilbene-diyl groups 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.
  • R is the same or different and represents 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, arylethyn
  • 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 the carbon atom 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.
  • 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.
  • 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 divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and the number of carbon atoms constituting the ring is usually about 3 to 60.
  • 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.
  • divalent heterocyclic group examples 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), Quinolinediyl groups represented by the following formulas (13-4) to (13-6), quinoxalinediyl groups represented by the following formulas (13-7) to (13-9), formulas (13-10) to ( 13-12) includes nitrogen as heteroatoms such as acridinediyl group represented by the following formula (13-13), bipyridyldiyl group represented by the following formula (13-13), and phenanthroline diyl group represented by the following formula (13-14)
  • 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.
  • R is the same as R in the arylene group.
  • Y represents O, S, SO, SO 2 , Se, or Te.
  • the formulas (12-1) to (12-23) It is the same.
  • the carbon atom may be replaced with a nitrogen atom, oxygen atom or 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 organic ligand usually has about 4 to 60 carbon atoms.
  • 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 its derivatives, porphyrin and its derivatives and the like.
  • Examples of the central metal of the metal complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
  • Examples of the metal complex having the organic ligand include low molecular fluorescent materials and phosphorescence. Examples of the material include known metal complexes and triplet luminescent complexes.
  • divalent group having the metal complex structure examples include groups represented by the following formulas (14-1) to (14-7).
  • R is the same as R in the arylene group.
  • the line attached to the apex of the ring structure means a direct bond as in the formulas (12-1) to (12-23).
  • 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.
  • 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.
  • o and p are the same or different and represent 0 or 1, and 0 ⁇ o + p ⁇ 1.
  • R is the same as R in the arylene group.
  • the line attached to the apex of the ring structure means a direct bond as in the formulas (12-1) to (12-23).
  • one structural formula has a plurality of Rs, but they may be the same or different.
  • R when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents. .
  • R in the substituent in which R includes an alkyl chain, they may be linear, branched or cyclic, or a combination thereof.
  • non-linear groups include, for example, isoamyl group, 2-ethylhexyl group 3,7-dimethyloctyl group, cyclohexyl group, 4-C1-C12 alkylcyclohexyl group and the like.
  • at least one alkyl chain having a cyclic or branched chain is contained.
  • a plurality of R may be connected to form a ring.
  • R when R is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom.
  • the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the structure of A is preferably formula (11-5), formula (12-9), formula (13-16), or formula (13-28).
  • At least one group of X 1 , X 2 , R 1 and R 2 in formula (1) and at least one group of X 3 and X 4 in formula (10) are polymerized. It has a repeating unit formed. That is, the following formula (16);
  • a dotted arc, a dotted line portion in a skeleton portion connecting a boron atom and a nitrogen atom, and an arrow from the nitrogen atom to the boron atom are the same as those in the formula (1).
  • X 1 ′, X 2 ′, R 1 ′ and R 2 ′ are the same as in formula (7), A is the same or different and represents a divalent group, and X 3 ′ and X 4 ′ are X 3 and X 3 in formula (10), respectively.
  • a boron-containing polymer having a structure of a repeating unit 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.
  • 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 three 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.
  • 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.
  • 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.
  • 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.
  • the boron-containing polymer of the present invention preferably has a weight average molecular weight of 10 3 to 10 8 .
  • a weight average molecular weight is in such a range, a thin film can be satisfactorily formed. More preferably, it is 10 3 to 10 7 , and still more preferably 10 4 to 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. Measurement was performed using a high-speed GPC apparatus: HLC-8220 GPC (manufactured by Tosoh Corporation). 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.
  • 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.
  • 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.
  • 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.
  • 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 to 99.9 mass% of a boron-containing compound represented by More preferably, it is 10 to 90% by mass.
  • the solid content concentration of the monomer component can be appropriately set within the 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).
  • 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.
  • X 3 and X 4 may be the same as the substituents having the reactive group in X 1 and X 2 described above.
  • a Wittig reaction causes a vinyl group and a halogen atom.
  • a Heck reaction in the case of a combination of an aldehyde group and a phosphonate methyl group, by a Horner reaction, in the case of a combination of a haloalkyl group and a haloalkyl group, by a dehydrohalogenation method, a sulfonium methyl group is obtained.
  • the polymerization can be carried out by a sulfonium salt decomposition method.
  • a halogen atom and a boryl group are obtained by a Knoevenagel reaction.
  • a Suzuki coupling reaction is performed.
  • a Grignard reaction is performed.
  • a zero-valent nickel catalyst is formed.
  • 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.
  • an oxidizing agent such as iron (III) chloride
  • the solvent used in the polymerization step is not particularly limited as long as the reaction proceeds.
  • water, N, N-dimethylformamide, N-methylpyrrolidone, dimethoxyethane can be used.
  • toluene, tetrahydrofuran, and xylene are preferable.
  • the solvent can use 1 type (s) or 2 or more types. Among these, in the case of the Wittig reaction, Horner reaction, and Knoevenagel reaction, N, N-dimethylformamide, tetrahydrofuran, dioxane, and toluene are preferably used.
  • a solvent having a relatively high boiling point such as N, N-dimethylformamide or N-methylpyrrolidone is preferably used.
  • N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran are preferably used.
  • 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.
  • it is preferable to fully deoxygenate so that reaction may advance in inert atmosphere.
  • this is not the case when the reaction is carried out in a two-phase system with water, such as the Suzuki coupling reaction.
  • a catalyst may be used.
  • 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
  • a catalyst is used.
  • 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.
  • These catalysts may use 1 type and may use 2 or more types. Among these, tetrakistriphenylphosphine palladium and tris (dibenzylideneacetone) dipalladium (0) are preferable.
  • the catalyst for performing the Grignard reaction the above-mentioned zero-valent palladium catalyst, divalent palladium salt catalyst and nickel catalyst are preferably mentioned.
  • 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.
  • the amount of the catalyst used is preferably 0.001 to 0.2 mol with respect to 1 mol of the boron-containing compound represented by the above formula (1).
  • 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, the amount is 0.005 to 0.15 mol, and still more preferably 0.01 to 0.1 mol.
  • 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-2-methylpropionamidine hydrochloride and azoisobutyronitrile; benzoyl peroxide, lauroyl Peroxides such as peroxide and cumene hydroperoxide can be used.
  • 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.
  • reducing agents such as sodium bisulfite, sodium sulfite, Mole salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid
  • amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, glycine, etc. You can also.
  • Each of these polymerization initiators and accelerators may be used alone or in combination of two or more.
  • the said polymerization initiator 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.
  • 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.
  • 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.
  • 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 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.
  • an alkali component may be added and the reaction may be performed in the presence of an alkali.
  • the reaction is preferably performed in the presence of an alkali.
  • the alkali component is not particularly limited.
  • 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.
  • 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.
  • 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.
  • a method of slowly adding the liquid 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.
  • it is more preferably 1 to 3 equivalents
  • 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.
  • the reaction can be allowed to proceed usually from about room temperature to about 150 ° C.
  • the reaction can proceed at about 80 to 160 ° C.
  • the reaction can be set according to the solvent, but the reaction is preferably carried out at 50 to 160 ° C.
  • 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.
  • the Wittig reaction 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.
  • the Heck reaction it may be about 1 to 100 hours.
  • the Suzuki coupling reaction it may be about 1 to 200 hours.
  • the polymerization reaction can be carried out either batchwise or continuously.
  • the amount of the Grignard reagent used is preferably equal to or greater than the monomer component. More preferably, it is 1 to 1.5 equivalents, and still more preferably 1 to 1.2 equivalents.
  • 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.
  • electrons injected from the cathode pass through the electron transport layer and reach the light emitting layer.
  • the minimum empty orbit (LUMO) of the material of the light emitting layer and the electron transport layer is used.
  • 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.
  • 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.
  • 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.
  • 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.
  • a light emitting device can be used suitably as members, such as a lighting fixture and a backlight for liquid crystal displays. That is, the illumination member formed using the light emitting device of the present invention is also one aspect of the present invention. Further, among the boron-containing compound and the boron-containing polymer of the present invention, those having an emission quantum yield of 20 to 100% can obtain stable emission due to 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.
  • Example 2 is a reaction formula showing the reaction of Example 1-1.
  • 2 is a reaction formula showing the reaction of Example 2-1.
  • 4 is a reaction formula showing the reaction in Example 2-34.
  • 4 is a reaction formula showing the reaction of Example 3.
  • 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.
  • 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.
  • the sample to be measured was placed in a quartz crucible, and the pressure was reduced to about 1 ⁇ 10 ⁇ 3 Pa, and the film was deposited to a thickness of 10 nm to obtain a measurement sample.
  • 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.
  • the ionization potential was measured using the ultraviolet photoelectron spectrometer (made by Kobelco Kaken).
  • the measured value was the energy level of the highest occupied orbit (HOMO) of the sample.
  • 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).
  • the absorption peak long wavelength side absorption edge ⁇ (unit: nm) of the absorption peak was read from the obtained spectrum, and the HOMO-LUMO gap (BG) was determined by the following formula (1).
  • ⁇ 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: 330-600nm ⁇ Luminescent quantum yield>
  • 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.
  • 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 boron triiodide in Example 1-1 was changed to boron tribromide, and boron complex 2 was obtained in a yield of 73%.
  • Example 1-1 (Reference Examples 1-1 to 1-4) The reaction was performed 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.
  • a boron complex 3 represented by the formula (145 mg, 0.45 mmol) was obtained in a yield of 89%.
  • the boron complex 4 represented by (150 mg, 0.44 mmol) was obtained with a yield of 89%.
  • the boron complex 5 represented by (40 mg, 0.082 mmol) was obtained in a yield of 28%.
  • the boron complex 6 represented by (85 mg, 0.23 mmol) was obtained with a yield of 75%.
  • 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., 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 boron complex 9 represented by the formula (210 mg, 0.37 mmol) was obtained in a yield of 73%.
  • Example 2 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.
  • 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.
  • 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%.
  • 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);
  • the boron complex 33 represented by (3.2 g, 8.4 mmol) was obtained with a yield of 70%.
  • the boron complex 34 represented by (3.5 g, 8.0 mmol) was obtained in a yield of 67%.
  • 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.
  • a boron complex 35 represented by the formula (2.2 g, 4.61 mmol) was obtained in a yield of 58%.
  • Example 2-2-7 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.
  • the boron complex 36 represented by (2.2 g, 4.61 mmol) was obtained with a yield of 58%.
  • 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%.
  • 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%.
  • 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 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 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 ): ⁇ 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 cooled thereto. , 24.9 mmol) is added dropwise with stirring. After stirring at room temperature for 1 hour, the mixture was diluted with toluene (30 ml), and 5-bromo-2- (4-bromo-2-dibromoborylphenyl) pyridine (3.3 g, 6.9 mmol) was added thereto at once.
  • THF tetrahydrofuran
  • the boron complex 42 represented by (350 mg, 0.62 mmol) was obtained in a yield of 9%.
  • 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%.
  • 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%.
  • 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 ⁇ l, 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.
  • 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%.
  • 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 ⁇ l, 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):
  • 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 ): ⁇ 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)
  • 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%.
  • 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.
  • the boron complex 50 represented by the formula (2.5 g, 3.97 mmol) was obtained in a yield of 33%.
  • 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 ): ⁇ 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., and at room temperature. Stir for 1 hour. To this was added 935 ⁇ l 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.
  • 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.
  • F8 boronic acid diester 140.3 mg, 0.251 mmol
  • tetrakistriphenylphosphine palladium 2.9 mg, 0.0025 mmol
  • 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.
  • the boron containing polymer F8B8 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8B8 was 80000.
  • the light emission quantum yield in a solution was 87%.
  • 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 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.
  • the boron containing polymer B8T2 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer B8T2 was 40000.
  • the light emission quantum yield in a solution was 29%.
  • 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.
  • the boron containing polymer B8P6 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer B8P6 was 60000.
  • the light emission quantum yield in a solution was 66%.
  • 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.
  • the boron containing polymer B8Cz represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer B8Cz was 22,000.
  • the light emission quantum yield in a solution was 74%.
  • 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.
  • the boron containing polymer B8TPA represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer B8TPA was 18000.
  • the light emission quantum yield in a solution was 60%.
  • 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.
  • B8 diester 140.5 mg, 0.251 mmol
  • tetrakistriphenylphosphine palladium 2.9 mg, 0.0025 mmol
  • 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.
  • the boron containing polymer PB8 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer PB8 was 11,000.
  • the light emission quantum yield in a solution was 49%.
  • BPhPr dibromide 350 mg, 0.62 mmol
  • F8 boronic acid diester 348 mg, 0.62 mmol
  • 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.
  • the boron containing polymer F8BPhPr represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8BPhPr was 10700.
  • 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.
  • Tetraethylammonium hydroxide (Et 4 NOH) 25 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, and the mixture was heated and stirred for 48 hours while refluxing at 115 ° C.
  • 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.
  • the boron containing polymer F8B8F represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8B8F was 126000.
  • BC6F5 dibromide represented by formula (337 mg, 0.51 mmol) and F8 boronic acid diester represented by 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.
  • 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.
  • bromobenzene 105 mg, 0.67 mmol
  • phenylboronic acid 294 mg, 2.41 mmol
  • 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.
  • the boron containing polymer F8BC6F5 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8BC6F5 was 126000.
  • 4,7-dibromobenzothiadiazole (129 mg, 0.44 mmol) was dissolved in 11 ml of toluene and stirred at room temperature for 10 minutes under 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.
  • the boron containing polymer F8B8BT represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8B8BT was 10800.
  • 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.
  • 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.
  • the boron containing polymer F8B8DBThO2 represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8B8DBThO2 was 8900.
  • 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 under a nitrogen atmosphere.
  • 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.
  • the boron containing polymer F8B8BT represented by these was obtained.
  • the weight average molecular weight of the boron-containing polymer F8B8BT was 25400.
  • 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.
  • the boron-containing polymer B8BT represented by this was obtained.
  • the weight average molecular weight of the boron-containing polymer B8BT was 118000.
  • 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 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.
  • 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.
  • 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.

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Abstract

La présente invention concerne un nouveau composé contenant du bore qui est utile en tant que matériau électroluminescent pour éléments EL organiques ou semi-conducteurs de type N ; un polymère contenant du bore obtenu au moyen dudit composé ; et un procédé de préparation dudit composé contenant du bore, qui permet la production à faible coût dudit composé contenant du bore et dudit polymère contenant du bore. L'invention porte en outre sur un matériau électroluminescent qui renferme un composé contenant du bore, doté d'un atome de bore et d'une double liaison et présentant une structure spécifique.
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CN102899027A (zh) * 2012-04-12 2013-01-30 杭州师范大学 一类含硼发光材料及其制备方法与应用
WO2013108024A1 (fr) * 2012-01-17 2013-07-25 The University Of Sheffield Composés aromatiques et procédés de fabrication desdits composés
CN103864831A (zh) * 2014-02-14 2014-06-18 上海工程技术大学 一种芳烃硼酸酯类化合物及其合成方法
US9450194B2 (en) 2012-12-28 2016-09-20 Idemitsu Kosan Co., Ltd. Heteroarene derivative and organic electroluminescence device using the same
JP2016199507A (ja) * 2015-04-10 2016-12-01 株式会社日本触媒 ホウ素含有化合物
WO2016207910A1 (fr) 2015-06-22 2016-12-29 Council Of Scientific & Industrial Research Organobores à quatre coordonnées de type chélate n,c offrant une accordabilité complète des couleurs
KR101775991B1 (ko) 2014-09-17 2017-09-07 이화여자대학교 산학협력단 보론-함유 유기반도체 화합물 및 이의 제조 방법
CN115772115A (zh) * 2023-02-10 2023-03-10 夏禾科技(江苏)有限公司 一种芳基吡啶溴代衍生物的合成方法

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WO2013108024A1 (fr) * 2012-01-17 2013-07-25 The University Of Sheffield Composés aromatiques et procédés de fabrication desdits composés
CN102899027A (zh) * 2012-04-12 2013-01-30 杭州师范大学 一类含硼发光材料及其制备方法与应用
CN102899027B (zh) * 2012-04-12 2014-03-12 杭州师范大学 一类含硼发光材料及其制备方法与应用
US9450194B2 (en) 2012-12-28 2016-09-20 Idemitsu Kosan Co., Ltd. Heteroarene derivative and organic electroluminescence device using the same
CN103864831A (zh) * 2014-02-14 2014-06-18 上海工程技术大学 一种芳烃硼酸酯类化合物及其合成方法
KR101775991B1 (ko) 2014-09-17 2017-09-07 이화여자대학교 산학협력단 보론-함유 유기반도체 화합물 및 이의 제조 방법
JP2016199507A (ja) * 2015-04-10 2016-12-01 株式会社日本触媒 ホウ素含有化合物
WO2016207910A1 (fr) 2015-06-22 2016-12-29 Council Of Scientific & Industrial Research Organobores à quatre coordonnées de type chélate n,c offrant une accordabilité complète des couleurs
US10301330B2 (en) 2015-06-22 2019-05-28 Council Of Scientific & Industrial Research N, C-chelate four-coordinate organoborons with full colourtunability
CN115772115A (zh) * 2023-02-10 2023-03-10 夏禾科技(江苏)有限公司 一种芳基吡啶溴代衍生物的合成方法

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