TW200925242A - Blue light-emitting polymer compound, organic electroluminescent device and use thereof - Google Patents

Abstract

Disclosed is a light-emitting material which is thermally more stable and exhibits high luminous efficiency and high durability when used as a blue light-emitting material for an EL device. Specifically disclosed is a blue light-emitting polymer compound characterized by containing a structural unit derived from a compound represented by the following formula (1). (1) (In the formula (1), R1-R4 and R11-R14 independently represent a hydrogen atom, a substituent or an electron-withdrawing substituent, and at least one of R1-R4 and at least one of R11-R14 independently represent an electron-withdrawing substituent; and R5-R8 and R15-R18 independently represent a hydrogen atom or a substituent.In this connection, one of R11-R18 is a substituent having a polymerizable carbon-carbon double bond.)

Description

200925242 IX. The present invention relates to a blue light-emitting polymer compound, and more particularly to a blue light-emitting phosphorescent polymer compound, and a compound using the same Electroluminescent device, method of making same, and use thereof. Φ [Prior Art] In recent years, in order to expand the use of organic electroluminescent elements (also referred to as "organic EL elements" in this specification), luminescent materials have been developed with high luminous efficiency and film forming properties. The phosphorescent polymer compound which is also excellent is specifically a polymer compound which is phosphorescent and contains a ruthenium complex structure in one of the main chain or the side chain. Among the above-mentioned phosphorescent polymer compounds, in the case of the blue light-emitting material, for example, JP-A-2003-2〇6320 (Patent Document 1), Q does not disclose that it has two phenylpyrroles in the side chain. A polymer material of a silver complex of a ligand and a picolinic acid ligand. However, there is still room for improvement based on the thermal stability of the material. Based on the thermal stability of the material, it has been reported that the 铱 complex with three phenylpyridine rings is preferred compared to the silver complex with two phenyl fluorene ratios. Patent Documents 1, 2). In JP-A-2003-119179 (Patent Document 2) and JP-A-2-68996 (Patent Document 3), a ruthenium complex having three phenylpyridine rings is disclosed, but it is not specifically disclosed. Color luminescent material · _. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Am. Chem. Soc. 1 25, 1 2971 (2003) Non-Patent Document 2: Okada Shinjiro, "Organic EL Material Technology", CMC Publishing, 2004, ρρ·206-214 ❹ [Summary of the Invention] Problem to be Solved The present invention has been made in view of such conventional techniques, and its object is to provide a kind of thermal stability and high luminous efficiency and durability when used as a blue light-emitting material of an EL element. Luminous material. Further, it is an object of the present invention to provide an organic EL device which has blue light emission and high luminous efficiency and high durability. Means for Solving the Problems The present inventors have made efforts to solve the above problems and have completed the present invention. The present invention is, for example, the following [1] to [13]. [1] A blue light-emitting polymer compound characterized by comprising a structural unit derived from a compound represented by the following formula (1); -5- 200925242 [Chemical Formula]

(1) In the formula (1), R1 to R4 and Rii to RM are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 to 4 Å. An aralkyl group, an amine group which may be substituted with an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a methylidene group which may be substituted with an alkyl group having 1 to 30 carbon atoms, or an electron attraction a substituent of the nature, the electron-attracting substituent may be an alkyl group selected from a halogen atom, substituted by fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted carbon number of 1 to 1 fluorene, and cyanide. a group, an aldehyde group, a fluorenyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 1 carbon atoms, an aminocarbonyl group having 1 to 1 carbon number, a thiocyanate group, and a carbon number of 1 to 10 The sulfonyl group, at least one of R1 to R4 and at least one of R11 to r14 are each independently a substituent of the electron attracting property, and R5 to R8 and R15 to R18 are each independently a hydrogen atom. , the base of carbon number 1~3〇, the square base of carbon number 6~20, the aromatic base of carbon number 7~40, the amine group which can be substituted by the alkyl group of carbon number 1~30, carbon number 1~ Alkoxy group of 30, or a methyl group which may be substituted with an alkyl group having 1 to 30 carbon atoms, In the R11~R18 1, lines having polymerizable carbon - carbon double bond of the substituent. [2] The blue light-emitting polymer compound according to the above [1], wherein the substituent is a fluorine atom, a fluorine-substituted carbon number of 1 to 10, and a fluorine-substituted one. An alkoxy group having 1 to 10 carbon atoms or an aryl group. [3] The blue light-emitting polymer compound according to [1] or [2] above, wherein in the formula (1), R1, R2, R" and R" are hydrogen atoms, r2, r4, R12 and R14. Is a fluorine atom. [4] The blue light-emitting polymer compound according to the above [1] or [2] wherein, in the formula (1), R1, R2, R4, R11, R13 and R14 are hydrogen atoms φ, R3 and R12. Is a fluorine atom. [5] The blue light-emitting polymer compound according to any one of the above [1] to [4], which further comprises a polymerizable compound which is transportable by a hole and/or a polymerizable compound which is electron transporting. Construction unit. [6] An organic electroluminescence device comprising: a substrate; an organic electroluminescence in which a pair of electrodes are formed on the substrate, and one or more organic layers of the light-emitting layer are interposed between the pair of electrodes; An element characterized in that the light-emitting layer contains a blue light-emitting non-conjugated polymer compound having a structural unit derived from a blue light-emitting compound represented by the following formula (1);

1 2 an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 40 carbon atoms. [In the formula (1), R1 to R4 and RM to R14 are each independently a hydrogen atom. , 200925242, an amine group capable of substituting an alkyl group having 1 to 30 carbon atoms, a rock alkoxy group, and a substituent capable of substituting an alkyl group having a carbon number of 1 to 30, and the substitution of the electron attracting property The group may be a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon number biO substituted by fluorine, an aldehyde group, a fluorenyl group having 2 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. 10 aminocarbonyl, thiocyanate and carbon sulfhydryl groups,

At least one of Ri to R4 and at least one of R11 to R14 are independently a substituent of the electron attracting property, and r5 to r8 and Rl5 to Rl8 are each independently an alkyl group of a hydrogen atom and have a carbon number of 6 to 20 An alkyl group substituted with an alkyl group having a carbon number of 7 to 40 and an alkyl group of 1 to 30, and a substituted alkyl group having a carbon number of 1 to 30, which may be substituted with an alkyl group having 1 to 30 carbon atoms, One of R11 to R18 has a polymerizable carbon base. [7] The organic electroluminescent device according to [6], wherein the substituent is a fluorine atom, a fluorine-substituted carbon number, a fluorine-substituted alkoxy group having a carbon number of 1 to 10, or a cyano group. . [8] The organic electroluminescence device according to [6] or [7] above, wherein, in (1), Ri, R3, rh, and Rn are hydrogen atoms, and r2 is

Rl4 is a fluorine atom. [9] The organic electroluminescence device according to the above [6] or [7], wherein, in (1), R1, R3, R4, R11, Ri3 and Ri4 are an alkylene group having 1 to 30 carbon atoms or substituted by fluorine. Alkyl, cyanide:oxycarbonyl, 1~10 sulfonate, each of which has a carbon number of 1 to 30: a group, a carbon. alkoxy group, or a carbon double bond. The alkyl group, through which the formula R4, R12 and the atom of the formula, R2 and 200925242 R12 are fluorine atoms. [10] The organic electroluminescence device according to any one of the above [6], wherein the blue light-emitting non-conjugated polymer compound further contains a polymerizable compound which is transported by a hole and/or A structural unit derived from an electron transporting polymeric compound. [11] A method of producing an organic electroluminescence device, comprising: forming at least one layer of an organic compound layer containing a high molecular compound of any one of the above [1] to [5] on an anode And a step of forming a cathode over the organic compound layer. [12] A screen display device comprising the organic electroluminescence device according to any one of [6] to [1]. [13] A seed surface light-emitting source characterized by comprising the organic electroluminescence device of any one of the above [6] to [10]. Effect of invention

According to the present invention, it is possible to provide a blue light-emitting material which has thermal stability and has high luminous efficiency and high durability when used as a light-emitting material of an EL element. Further, according to the present invention, an organic EL element having blue light emission and high luminous efficiency and high durability is provided. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 200925242 In addition, in the present invention, the term "blue luminescence" does not necessarily have a specific P ' "but, for example, indicates that the wavelength of the maximum luminescence intensity in the luminescence spectrum is 480 nm or less, preferably 475 nm or less. In terms of. [Blue light-emitting polymer compound] The blue light-emitting polymer compound of the present invention, which is a blue light-emitting phosphorescent polymer compound, is characterized by containing the following formula (1) a structural unit derived from a compound (hereinafter also referred to as "compound (1)");

In the formula (1), R1 to R4 and R11 to R14 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aromatic group having 7 to 40 carbon atoms. An amine group which may be substituted with an alkyl group having 1 to 30 carbon atoms, a oxy group having 1 to 3 carbon atoms, a methylidene group which may be substituted with an alkyl group having 1 to 30 carbon atoms, or a halogen atom, Fluorine-substituted carbon number alkyl group, fluorine-substituted carbon number 1 to 1 alkoxy group 'cyano group, aldehyde group, carbon number 2 to 10 fluorenyl group, carbon number 2 to 10 alkoxycarbonyl group' a substituent of an electron attracting group having a carbon number of an aminocarbonyl group, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms, at least one of R1 to R4 and at least 1 of R1丨~!^4 Each of the groups is a substituent of the electron attraction, and R5 to R8 and R15 to R18 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 6 to 2 0. An aryl group, an aralkyl group having 7 to 40 carbon atoms, an amine group substituted with an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms a substituted methyroalkyl group, but one of Rn-R18 has a polymerizable carbon-carbon The double bond is taken as the base. φ In the above R1 to R8 and R15 to R18, the alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl , t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, adamantyl, etc. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl and octyl are preferred. The aryl group having 6 to 20 carbon atoms may, for example, be a phenyl group, a tolyl group, a xylyl group, a fluorenyl group, a naphthyl group, a fluorenyl group or a pyridyl group, and is a phenyl group, a tolyl group, a xylyl group and a fluorenyl group. It is better. The aralkyl group having 7 to 40 carbon atoms may, for example, be a benzyl group, a phenylethyl group, a 2-phenylethyl group, a 2-(1-phenyl)propyl group or a 3,3·diphenylpropyl group. It is preferred to use a benzyl group. The above-mentioned amine group which may be substituted with an alkyl group having 1 to 30 carbon atoms, for example, an amine group, a dimethylamino group, a diethylamino group, a dibutylamino group or the like, and preferably a dimethylamino group. . The above-mentioned alkoxy group having a carbon number of 1 to 30, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy 'isobutoxy group, a sec-butoxy-11-200925242 group, t A -methoxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group or the like is preferred, and a methoxy group is preferred. The above-mentioned carboxyalkyl group which may be substituted with an alkyl group having 1 to 30 carbon atoms, for example, trimethylmethanyl group, triethylmethane alkyl group, t-butyldimethylformyl group, trimethoxy formyl group Etc., and trimethylmethanyl group is preferred. Further, in the above R1 to R4 and R" to R14, the electron-attracting substituted φ group may be, for example, a halogen atom, an alkyl group having a carbon number of 1 to 1 fluorene substituted by fluorine, and a carbon number of 1 to 10 substituted by helium. Alkoxy group, cyano group, aldehyde group, a carbon number of 2 to 10, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aminocarbonyl group having a carbon number, a thiocyanate group, and a carbon number of 1 to 10 Sulfonyl. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or a moth 'atom', and a fluorine atom is preferred. The alkyl group having 1 to 1 carbon atom substituted by fluorine is, for example, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and a trifluoromethyl group is preferred. An alkoxy group having a carbon number of 1 to 10 substituted by fluorine, #!! If there is fluoromethoxy oxime, -fluoromethoxy, trifluoromethoxy, :!, 〗, 2,2·tetrafluoro ethoxy A 1,1,2,2,2-pentafluoroethoxy group or the like is preferred, and a trifluoromethoxy group is preferred. The fluorenyl group having 2 to 1 carbon atoms is preferably an ethyl fluorenyl group, a propyl fluorenyl group, or a fluorenyl group. The alkoxycarbonyl group having 2 to 10 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a t-butoxycarbonyl group, a benzyloxy group, a phenoxycarbonyl group, etc. A methoxycarbonyl group, a t-butoxycarbonyl group, and a benzyloxycarbonyl group are preferred. -12- 200925242 The aforementioned aminocarbonyl group having a carbon number of 1 to 10 is, for example, an aminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dibutylamino group, or the like, and is a dimethylamine. A carbonyl group is preferred. The sulfonyl group having 1 to 10 carbon atoms is, for example, a methylsulfonyl group, an ethylsulfonyl group or a phenylsulfonyl group, and a methylsulfonyl group and a phenylsulfonyl group are preferred. In the above-mentioned electron-attracting substituent, in the substituents, the light-emitting wavelength of the radical H in the ruthenium complex is shorter, the luminescent color has a blue color with high color purity, and the luminescence quantum yield is high, It is preferably a fluorine atom, an alkyl group having 1 to 10 carbon atoms substituted by fluorine, an alkoxy group having 1 to 10 carbon atoms substituted by fluorine, and a cyano group, and preferably a fluorine atom. In the compound (1) of the present invention, at least one of R1 to R4 and at least one of 'R11 to R14 are the electron-attracting substituents, compared to: only R1 to R4. At least one of them, or at least one of R11 to R14, is a blue light-emitting person having a higher color purity for the electron-attracting substituent. The substituent having a polymerizable carbon-carbon double bond (hereinafter also referred to as "polymerizable substituent"), and the polymerizable substituent has, for example, a propyl group, an alkenyl group (vinyl group, 2-propenyl group, etc.). Styryl group, propylene fluorenyloxy group, methyl propyl decyl oxy group, propyl amide group, methyl propyl amide group, and maleic anhydride amide group (preferably vinyl, benzene) Substituents for vinyl, acryloyloxy and methacryloxy). The polymerizable substituent may have a divalent group at a position between the carbon atom of the phenylpyridine ring and the polymerizable substituent which is 铱-coordinated (hereinafter, -13, 2009, 242, also referred to as "spacer") ). The spacer may be, for example, a linear or branched saturated hydrocarbon chain or a hydrocarbon chain containing a hetero atom. Wherein, the hydrocarbon chain containing the aforementioned hetero atom means that one or two or more non-adjacent methyl groups in the saturated hydrocarbon chain are - 可以-, -CO-, -CO-0-, - 0-C0-, -0-C0-0- '-CO-NH- ' -NH-CO- ' -O-CO-NH- > -NH-C0-0-, -NH-, -N(CH3 a saturated hydrocarbon chain substituted with -N(C6H5)-, -S-, -SO-, -S〇2_, -CH=CH-, -CsC-, -C=N-, and the like. The number of atoms included in the longest chain of the spacer is preferably 1 to 5, based on the fact that the q-position is closely bound to the polymer backbone. The polymerizable substituent 'is, for example, a group represented by the following chemical formulas (al) to (a41). Among these polymerizable substituents, (al), (a6), (a9) to (al9)' or (a2 4) are based on the viewpoint that the organic light-emitting element has high luminous efficiency and the luminance is halved for a long time. The base shown by ~(a3 0) is preferred; and is represented by (al), (al2)~(al9), (a24), (a25), (a28), (a29) or (a30) The base is the best. e [4] ·_/ ♦乂,乂(a1) (a2) (a3) (a4) (a5) (a6) (a7) (a8) ·-〇- (a9) (a10) (a11) ( a 12) 200925242

(a13)

〇, ο (a21)

(a24) (a25)

(a30)

(a23)-IK (327)

(a31) (a32)

(a33) (a34)

Ch3(a35)

(a36) -15- 200925242

(a37) (a38)

(a40) (a41) When a polymerizable substituent of BIJ is bonded to a phenyl group of a phenyl fluorene ratio B, a steric hindrance occurs between the polymerizable substituent and the electron-attracting substituent, resulting in a compound (1) The polymerizability is lowered, and the control of the polymerization reaction is difficult. Sometimes it is impossible to synthesize a polymer having a sufficient molecular weight. Based on the above, the compound (1) is preferably a compound in which one of R15 to R18 is the polymerizable substituent. Further, when R15 is the above-mentioned polymerizable substituent, steric hindrance occurs between the polymerizable substituent and the phenyl group of the phenylpyridine ring of the compound (1); and when R18 is the aforementioned polymerizable substituent A steric hindrance occurs between the polymerizable substituent and the ruthenium atom, and the polymerizability is lowered. The compound having R16 or R17 as the polymerizable substituent is preferred. ® The above compound (1) is based on the fact that the light-emitting wavelength is shorter, the luminescent color has a blue color with high color purity, and the luminescence quantum yield is high, which is a hydrogen atom of R1, R3, R11 and R13, and R2 A compound represented by the following formula (2) (hereinafter also referred to as "compound (2)")) is preferred as the compound of the fluorine atom of R4, R12 and R14. 200925242 [Chem. 6]

(2) Further, in the compound (2), based on the fact that the light-emitting wavelength is shorter, the luminescent color has a high color purity, and the R6-based carbon number is 1 to 30 alkyl or carbon. A compound having 1 to 30 alkoxy groups is preferred. The above compound (1) is based on the viewpoint of high luminescence quantum yield, which is a compound of R1, R3, R4, R", R13 and R14 hydrogen atoms, R2 and R12 system; fluorine atom (the following formula (3) The compound shown (hereinafter also referred to as "compound (3)"))) is preferred.

Further, in the compound (3), the alkyl group having a carbon number of 1 to 30 or the carbon number of 1 to 3 is based on the fact that the luminescent color has a blue color with a high color purity. A compound of 0 alkoxy group is preferred. In addition, the compound (1) may be used alone or in combination of two or more. -17- 200925242 Method for Producing Compound (1) The above compound (1) can be produced, for example, by the following method. First, as shown in the following figure, a phenylboronic acid derivative and a 2-dehalogenated pyridine derivative are reacted by a usual Suzuki coupling reaction to obtain a phenyl succinyl derivative (1-1). Further, commercially available reagents can be used as the phenylboronic acid derivative and the 2-halogenated pyridine derivative. Further, the 2-pyridine halide derivative ' can also be obtained by halogenating a commercially available pyridine derivative according to a general method.

Next, ruthenium (III) chloride trihydrate and the following phenylpyridine-derived ruthenium (1-1) [Chemical 9]

It is 50 to 150 in a mixed solvent of an alcohol and water. (: heating to cause a reaction, and the following dinuclear complex (1-2) -18 - 200925242 [1-2] (1-2) is obtained. Next, in the formula (1-1) and RkR8 in 1-2), each of which is synonymous with R1 to R8 in the formula (1), and the aforementioned alcohols are, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 2-methoxybutanol, 2-ethoxybutanol, ethylene glycol, 1,2-propanediol, H propylene glycol, 1,3-butanediol, l, 4 - butanediol, diethylene glycol, diethylene glycol monomethyl ether, etc. The ratio of the alcohol to water (alcohol: water (volume ratio)) in the mixed solvent is, for example, 1 to 9:1. A specific example of the above mixed solvent is, for example, a mixed solvent of 2-ethoxyethanol and water (2-ethoxyethanol: water = 3:1 (volume ratio)). Further, the reaction time is, for example, 30 minutes.

~1 2 0 0 hours. Next, the following phenylpyridine derivative (1-3) in the dinuclear complex and a substituent having a polymerizable carbon-carbon double bond;

R13 RHR15 r16 (1-3) and in the presence of a base and/or a silver salt, by heating in 50 to 200 ° C in a solution of toluene or mesitylene, such as -19-200925242, Compound (1). Next, in the formula (1-3), R11 to R18, each of which is synonymous with R11 to R18 in the formula (1). The base may, for example, be an inorganic compound such as sodium carbonate or potassium carbonate, or an organic base such as tributylamine or lutidine. Further, the aforementioned silver salt 'for example, silver oxide (I), silver sulfide (〗), silver sulfate (I), silver nitrate (I), silver (I) phosphate, silver acetate (I), silver trifluoroacetate (I) Silver (I) p-toluenesulfonate, silver (I) methanesulfonate, silver (I) trifluoromethane φ sulfonate, and the like. Further, the reaction time is, for example, 10 minutes to 48 hours. Structural unit derived from a charge transporting polymerizable compound The polymer compound of the present invention may further contain a structural unit derived from a hole transporting polymerizable compound and/or an electron transporting polymerizable compound. . Further, in the present invention, the hole transporting polymerizable compound and the electron transporting polymerizable compound are collectively referred to as a charge transporting polymerizable compound. The polymer compound of the present invention preferably contains one or two or more kinds of structural units derived from a hole transporting polymerizable compound, or one or two or more kinds of electron transporting polymerization. A polymer compound of a structural unit derived from a compound. When such a polymer compound is used, since the degree of mobility of charges in the light-emitting layer is high and a homogeneous film can be formed by coating, a high luminous efficiency can be obtained. In addition, the polymer compound of the present invention preferably contains one or two or more kinds of structural units derived from a polymerizable compound having a hole transporting property, and one or two or more kinds of electron transporting properties. Polymerizable compound -20- 200925242 A polymer compound of a structural unit derived from a substance. When such a compound is used, since the polymer compound has a function of hole transportability and transportability, holes and electrons can be more efficiently in the vicinity of the structural unit derived from the phosphorescent luminescence represented by the above formula (1). For the sake of the ground, higher luminous efficiency can be obtained. The polymerizable compound of the above-mentioned hole-transporting property and the above-mentioned electron-transporting polymerizable compound are not particularly limited as long as they have a substituent having a radical polymerizable polymer group, and a conventional compound can be used. Examples of the polymerizable functional group include an allyl group, an alkenyl group (e.g., an ethyl 2-propenyl group), an acryloyloxy group, a methacryloyloxy propylene fluorenyloxyethyl urethane group, and the like. a urethane (acryloyloxy group, propenyl decylamino group, methacryl decyl decyl fluorenylamino group, maleic anhydride imienimine group, and derivatives thereof, etc. More preferably, when the polymerizable functional group is a alkenyl group, the substituent of the radical polymerizable functional group is represented by the following formulas (A1) to (A12). The substituent is preferably a group represented by the following formulas (Al), (A5), (A8), and (A12), which can easily introduce a polymerizable functional group into charge transportability. It is most desirable. The polymer electron transport compound is combined with the transferable functional charge to the alkenyl group, methyl methyl) group, and B. These include the above-mentioned general, and the compound is replaced by -21 - 200925242 [Chemical 12] ΌΗ ch3

CH3 a S

HaC ch3 ,ch2 — (A3) mC 一气 CH2 {A4) ^ (A1)

CH2 (A2)

HzC

(A5)

CH\h2 (A12) The polymerizable compound of the above-mentioned hole transport property is specifically a compound represented by the following general formulas (E01) to (E09), and is based on the viewpoint of the luminous efficiency of the organic EL device. The compound represented by the following formula (E02) or (E03) is preferred. -22- 200925242 [Chem. 13]

E01 E02 E03

Specifically, the electron transporting polymerizable compound is preferably a compound represented by the following general formulas (E10) to (E19), and based on the luminous efficiency of the organic EL device, the following formula is used ( The compound represented by E16) or (E 1 9 ) is preferred. -23- 200925242

E18 E16 E17

In the above formulae (E01) to (E19), the substituent represented by the above formula (Al)-24-200925242 is substituted with a substituent represented by the above formula (A2) to (A12). In view of the fact that the functional group can be easily introduced into the polymerizable compound, a compound having a substituent represented by the above formulas (A1) and (A5) is preferred. Among these, the best ones are used as a compound represented by any one of the above formulas (E02) and (E03) as the polymerizable polymerizable material, and as the electron transport property. A compound represented by any one of the above formulae (E16) and (E19) of the polymerizable compound 0. When such a polymerizable compound is used, an organic EL device having high luminous efficiency and high durability can be obtained. Blue light-emitting polymer compound The blue light-emitting polymer compound of the present invention may be a so-called oligomer compound or a polymer compound. The weight average molecular weight of the polymer compound of the present invention is preferably from 1,000 to 5,000,000, more preferably from Φ 2,000 to 1,000,000, most preferably from 3,000 to 1 Torr. The molecular weight in the present specification means a molecular weight in terms of polystyrene measured by a GPC (Gel Penetration Chromatography) method. When the molecular weight is within this range, it is preferred because the polymer is soluble in an organic solvent and a uniform film can be obtained. The ratio of the compound represented by the above formula (1) (the ruthenium complex) and the charge transportable polymerizable compound (the polymerizable property of the hole transporting property and/or the electron transport property) can be appropriately set. A desired blue light-emitting polymer compound is obtained, and the polymer compound may be any of a random total of -25-200925242 polymer, a block copolymer, and an interactive copolymer. In the polymer compound of the present invention, the compound 1 and any of the charge transporting polymerizable compounds are polymerized by polymerization of each of the polymerizable carbon-carbon double bonds and the radical polymerizable functional group. Each structural unit is a non-conjugated, non-conjugated polymer compound. In the polymer compound of the present invention, the number of structural units derived from the compound represented by the above formula (1) (the ruthenium complex) is defined as m', and the number of structural units derived from the charge-transporting polymerizable compound (electricity) The total number of structural units derived from the polymerizable compound of the hole transporting property and/or the electron transporting property is η (when m and η are integers of 1 or more), and the structure of the above-described ruthenium complex is derived from the number of pre-structural units. The ratio of the number of units, i.e., m/(m + n), is preferably in the range of 0.001 to 0.5, and is preferably in the range of 0.001 to '0.2. When m/(m+n) is in this range, the charge mobility is high, and the influence of concentration extinction is small, and an organic EL element having high luminous efficiency can be obtained. In addition, when the polymer compound of the present invention contains a structural unit derived from a polymerizable compound of a hole transporting property and a structural unit derived from an electron transporting polymerizable compound, for example, polymerization of hole transportability The number of structural units derived from the compound is X, and when the number of structural units derived from the electron transporting polymerizable compound is y, the relationship between X and y and the above η is established as n=x+y. The number of structural units derived from the polymerizable compound of the charge transporting property is the optimum ratio of the number of structural units derived from the polymerizable compound of the hole transporting property, and the electron transporting polymerizable compound. The optimum ratio of the number of structural units derived y/n -26- 200925242 is determined according to the charge transport energy of each structural unit, the charge transportability of the structural unit derived from the ruthenium complex, and the concentration. When the polymer compound of the present invention is used as the only compound for forming a light-emitting layer of an organic EL device, χ/η and y/n are preferably in the range of 0.05 to 0.95, and in the range of 0.20 to 0.80. For the best. In addition, x/n+y/n=l is established. Further, the polymer compound of the present invention may further contain a structural unit derived from another polymerizable compound insofar as it does not contradict the object of the present invention. Such a structural unit is, for example, a compound having no charge transporting property such as alkyl (meth)acrylate such as methyl acrylate or methyl methacrylate, styrene or a derivative thereof, but is not limited thereto. The scope. The polymerization method of the polymer compound of the present invention is preferably a radical polymerization. Therefore, a preferred polymerization method of the polymer compound of the present invention, for example, a method in which at least the compound represented by the above formula (1) is polymerized in the presence of a radical polymerization agent; a compound represented by the above formula (1) and a polymerizable compound of the above-mentioned hole transporting property of X mole and/or a polymerizable compound of the electron transporting property of y mole, in a radical polymerization initiator a manufacturing method for polymerizing in the presence thereof; (only, m, x, and y, each of which is an integer of 1 or more; m/ (m+x+y), preferably 〇.〇〇1 to 〇5, The optimum is 0.001-0.2; -27-200925242 x/(x+y) and y/(x+y), each of which is preferably 〇·〇5~0.95, and the best system is 0.20~0.80.) The radical polymerization initiator may, for example, be dimethyl-2,2'-azobis(2-methylpropionate) or the like. Organic EL device The organic EL device of the present invention is an organic electroluminescence having a substrate, a pair of electrodes formed on the φ substrate, and a layer or layers of an organic layer containing a light-emitting layer between the pair of electrodes. An element characterized in that the light-emitting layer contains a blue light-emitting non-conjugated polymer compound having a structural unit derived from a blue light-emitting compound represented by the following formula (1) (that is, the above-described polymer compound of the present invention) ):

The blue light-emitting compound represented by the above formula (1) and the polymer compound having a structural unit derived from the compound are as detailed (e.g., preferred) as described above. Further, the method for producing an organic EL device of the present invention comprises the steps of: forming at least one layer of an organic compound layer containing the above-described polymer compound of the present invention on an anode; and 'in the organic compound-28- 200925242 The step of forming a cathode on the layer. The configuration of the organic EL device of the present invention is shown in Fig. 1. The arrangement of the organic EL device of the present invention is set between (6) on the transparent substrate (1). The layer (φ and the electron transport layer (5). Between the organic EL (2) and the cathode (6), 1) 霄 2) any of the light-emitting layer/electron transport layer. 3)) containing the hole transporting material, the luminescent material 3 layers, 4) containing the hole transporting material, the luminescent material meter material, and the electron transporting material layer, 6), or the luminescent layer may be laminated 2 A hole injection layer may be provided between the layer above and the light-emitting layer (4) between the hole injection layer Q and the cathode (6). Light Emitting Layer The method for forming the light emitting layer is not specifically formed as follows. First, a solution of (A) a light-emitting polymer compound and a charge transporting property or (B) a solution in which a blue substance of the present invention containing a structural unit derived from a chemical is dissolved is prepared. An example of this is shown in Fig. 1, and is not limited to this range. The anode (2) and the cathode 3), the light-emitting layer (4), and the element, for example, may be provided on the anode I-hole transport layer/light-emitting layer, or may be provided with only one layer of the layer of the electron transport material, 5 Any one of the luminescent layers. Further, in the anode (2) or in the light-emitting layer (4), for example, a polymerizable color-emitting polymer compound capable of dissolving the blue non-conjugated polymer compound of the present invention can be dissolved. 29 200925242 A non-conjugated polymer compound having a charge transport property contained in the solution (A) can be a known polymer compound, for example, a polymerizable compound containing the above-mentioned hole transporting property and/or the above-mentioned electrons can be used. A non-conjugated polymer compound of a structural unit derived from a transportable polymerizable compound. The solvent to be used in the preparation of the solvent is not particularly limited, and examples thereof include a chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or anisole, or a toluene or xylene. Examples of the aromatic hydrocarbon-based solvent, a ketone solvent such as acetone or methyl ethyl ketone, and an ester solvent such as ethyl acetate, butyl acetate or ethyl cellosolve acetate. Next, the solution thus prepared is formed into a film on a substrate by an inkjet method, a spin coating method, a dip coating method, a printing method, or the like. The concentration of the above-mentioned solution is determined depending on the compound to be used, the film formation conditions, and the like, and the 'in the case of the spin coating method or the dip coating method is preferably 0.1 to 10% by weight. Thus, since the light-emitting layer can be easily formed into a film, in addition to the object of simplification in the manufacturing steps, the elements can be enlarged. <Other Materials> Each of the above layers ' can be formed by mixing a polymer material as a binder. The polymer material 'e.g., polymethyl methacrylate, polycarbonate, polyester, polyfluorene, polydiphenyl ether or the like. Further, the materials used in the above respective layers may be mixed with materials having different functions, such as luminescent materials, hole transporting materials, electron transporting materials, etc., and -30-200925242 forms each layer. Even if the polymer compound of the present invention and the non-conjugated polymer compound are contained in the organic layer, other hole transporting materials and/or electron transporting materials may be further contained for the purpose of supplementing the charge transporting property. Such a transport material may be a low molecular compound or a polymer compound. The hole transporting material forming the hole transporting layer or the hole transporting material mixed in the light emitting layer, for example, TPD (N, N'-dimethyl-N, N'-(3-methyl 0 phenyl)-1 , 1 biphenyl-4,4,-diamine); a-NPD (4,4,-bis[N-(1-naphthyl)-fluorenyl-phenylamino]biphenyl); m-MTDATA a low molecular triphenylamine derivative such as (4,4', 4M-tris(3-methylphenylphenylamino)triphenylamine); polyvinylcarbazole; derived from the aforementioned triphenylamine A polymer compound in which a polymerizable substituent is introduced into a substance to be polymerized; a fluorescent light-emitting polymer compound such as polyparaphenylene or polydialkylfluorene. The polymer compound of the above-mentioned high molecular compound is, for example, a polymer compound of a triphenylamine skeleton disclosed in JP-A-8-157575. The above-mentioned hole transporting materials may be used alone or in combination of two or more kinds, and may be used by laminating different hole transport materials. The thickness of the material to be transported by the hole is determined by the conductivity of the hole transport layer, etc., but it is preferably 1 nm~5 #m, more preferably 5 nm~1; /m, the best is 1〇I1m~500 nm. The electron transporting material forming the electron transporting layer, or the electron transporting material mixed in the light emitting layer, for example, a quinolinol derivative metal complex such as Alq3 (8-hydroxyquinoline aluminum) or the chelate derivative a low molecular compound such as a triterpene derivative, a hydrazine derivative, a triazine derivative or a triarylborane derivative; a polymer compound in which a polymerizable substituent is introduced into the above-mentioned low molecular compound to be polymerized in -31 - 200925242 Wait. The polymer compound is, for example, a poly PBD disclosed in Japanese Laid-Open Patent Publication No. Hei 10-1665. The above-mentioned electron transporting materials may be used singly or in combination of two or more kinds, or may be used by laminating different electronic transport materials. The thickness of the electron transport layer is determined by the conductivity of the electron transport layer, etc., but it is not limited, but preferably 1 nm to 5//m, more preferably 5 nm to l/zm, and most preferably 10 nm to 500 nm ° 0 In addition, based on the case where the hole is passed through the light-emitting layer near the cathode side of the light-emitting layer, and the hole and the electron are efficiently recombined in the light-emitting layer, a hole block can be provided. Floor. In order to form the above-mentioned hole/block layer, a conventional material such as a conventional triazole derivative, an oxadiazole derivative or a phenanthroline derivative can be used. The hole injection layer may also be provided between the anode and the light-emitting layer to ease the injection barrier during the hole injection. In order to form the above-mentioned hole injecting layer, a conventional material such as copper phthalocyanine, a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonate (PSS), or a fluorinated hydrocarbon can be used. Between the cathode and the electron transport layer, or between the cathode and the cathode adjacent to the cathode layer, an insulating layer having a thickness of 0.1 to 10 nm may be provided for improving the electron injection efficiency. In order to form the above insulating layer, a conventional material such as lithium fluoride, magnesium fluoride, magnesium oxide or aluminum oxide can be used. Examples of the method for forming the ruthenium transport layer, the light-emitting layer, and the electron transport layer (film formation method) include a resistance heating vapor deposition method, an electron beam evaporation method, a sputtering method, an inkjet method, a spin coating method, and a printing method. , spraying method, dispensing coating method, and the like. In the case of a low molecular compound, it is preferable to use a resistance heating vapor deposition method -32-200925242 or an electron beam evaporation method, and in the case of a polymer compound, an inkjet method, a spin coating method, or a printing method is suitably used. Anode The anode material 'for example, a conventional transparent conductive material such as ITO (indium tin oxide), tin oxide, zinc oxide 'polythiophene, polydash, polyaniline or the like can be used. The surface resistance of the Q electrode formed by such a transparent conductive material is preferably 1 to 50 Ω / □ (ohm/square). The thickness of the anode is preferably 50 to 300 nm. As the method for forming the precursor material (film formation method), for example, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like can be used. For the cathode material of the cathode, for example, an alkali metal such as Li, Na, K, or Cs; an alkaline earth metal such as Mg, Ca, or Ba; Ai; a MgAg alloy; A1 of AlLi, 〇A1Ca, and an alkali metal or alkaline earth metal; A conventional cathode material such as an alloy. The thickness of the cathode is preferably from 10 nm to lym, and most preferably from 50 to 500 nm. When a highly active metal such as an alkali metal or an alkaline earth metal is used as the cathode, the thickness of the cathode is preferably 0.1 to 1 〇〇 nm, preferably 0.5 to 50 nm. Further, at this time, based on the protection For the purpose of the cathode metal, a metal layer that is stable to the atmosphere can be 'laminated on the cathode. The metal forming the metal layer is, for example, Al, Ag, Au, Pt, Cu, Ni, Cr or the like. The thickness of the metal layer is preferably 10 nm to 1/zm, and most preferably 50 to 500 to 33 to 200925242. The method for forming the cathode material (film formation method), for example, resistance heating evaporation method, electron beam evaporation Method, sputtering method, ion plating method, and the like. In the substrate of the organic EL device of the present invention, an insulating substrate transparent to the light-emitting wavelength of the light-emitting material can be used, and in addition to glass, PET (polyethylene terephthalate), polycarbonate, or the like can be used. Transparent plastic silicone and so on. Use of the organic EL device of the present invention is preferably a conventional method using a matrix method or a segmental pixel on a screen display device. Further, the above-mentioned organic EL element may be applied to a surface emitting light source without forming a pixel. The organic EL device of the present invention is specifically suitable for use in a display device such as an electric camphor, a television, a portable terminal, a mobile phone, a car navigation, a viewing window of a video camera, a backlight, an electronic photograph, an illumination source, Record light source, exposure light source, reading light source, logo, kanban, interior, optical communication, etc. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the examples. -34- 200925242 <Measurement device, etc.>

1) 'H-NMR ' 13C-NMR JNM EX270 270Mz by JEOL Ltd. 2) Mass Analysis (FAB-MS)

Japan Electronics Co., Ltd. Automass II 3) Elemental Analysis CHNS-932 type manufactured by RECO Corporation φ 4 ) GPC measurement (molecular weight measurement)

Shodex GPC-101 Column: Shodex GPC LF-804x3

Isolation liquid: tetrahydrofuran temperature: 40 °C 'Detector: differential refractive index detector 5) ICP emission analysis (unit) ICPS-8000 manufactured by Shimadzu Corporation 合成 [Synthesis Example 1] Synthesis of polymerizable ruthenium complex (A) [Chemistry 16]

Ιϊα3.3Η2〇F - Bu^ethcxyethanol, Η^Ο (W) Refer to the above procedure for explanation 35- 200925242 <Synthesis of Compound (W)> In Dimrod's cooling tube and 50 with three-way valve In a two-neck flask of ml, 2-(2,4'-difluorophenyl)-4-tri-butylpyridine 371 mg, chlorinated by the method described in Polyhedron 25, 1 1 67 (2006)铱(III) trihydrate 2 12 mg, 2-ethoxyethanol 9 ml, pure water 3 ml, nitrogen gas was added to the obtained solution for 5 minutes, and then stirred under nitrogen for 14 hours and refluxed. Carry out the reaction. After the reaction, the mixture was cooled to room temperature, and 30 ml of pure water was added to precipitate a product. The precipitate was collected by filtration, washed with 50 ml of a mixed solution of methanol/water = 7/3, and dried under reduced pressure to give a yellow powdery compound (W). The yield was 367 mg and the yield was 85%. The powder 'end is not identified and is used directly in the following steps. [Chem. 17]

-36 - 200925242 Please refer to the above procedure for explanation. <Synthesis of Compound (A1)> In a Dimrod's cooling tube and a three-necked flask having a three-way valve, '6-chloro DJ±D--3-carbonate was added (1.416 g, 1 〇.〇mmol). , 2,4-difluorophenylboronic acid ( 1.895 g, 12.0 mmol), sodium carbonate (2.12 g, 20·0 mmol), 1,2-dimethoxyethane (30 ml), and pure water ( 10 0 ml), pumped with nitrogen. Further, tetrakis(triphenylphosphine)palladium (ruthenium) (231 mg '0.2 mmol) was added, and the mixture was stirred for 2 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature. After adding chloroform, the organic layer was washed with a sodium chloride aqueous solution. The obtained organic layer was dried over magnesium sulfate, and then filtered and evaporated. The residue was purified by hydrazine gel column chromatography (solvent: liquid: chloroform/hexane = 1/1 to chloroform, gradient), and dried under reduced pressure to afford compound (A1) as a white solid. The yield was 1.730 g and the yield was 79%. The result of the identification of the compound (A1) is shown below. 10 ^-NMR ( 270 MHz > CDC 13 ) ppm : 10.17 ( s > 1H > -CHO ), 9.15 ( d > 1H, J = 2.2 Hz, 8.24 ( dd, 1H, J = 8.2, 2.3 Hz, ArH ), 8 · 16 ( m ' 1H, A r H ) , 7.97 ( d, 1H, J = 8.4Hz, ArH) , 7.0 5 ( m, 1H, Ar H ) , 6.96 ( m, 1H, ArH ). Synthesis of Compound A2> In an eggplant-shaped flask having a three-way valve, Compound A1 (438 mg' 2.0 mmol) was added and replaced with nitrogen, and then dehydrated THF (4 - 37 - 200925242 ml) was added thereto, and then slowly 3M methylmagnesium bromide diethyl ether solution (0.73 ml, 2.2 mmol) was added, and the mixture was stirred at room temperature for 4 days to cause a reaction. After the reaction, pure water was carefully added and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, and then filtered, and the solvent was evaporated. The residue was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc The solvent was distilled off, and dried under reduced pressure to give Compound (A2) as a colorless liquid. The yield was 465 mg, and the yield was Q 99%. The compound (A2) was identified as follows: !H-NMR ( 270MHz > CDC13 ) ppm : 8.69 ( d,1H, J=1.9Hz, ArH) , 7 · 99 ( m,1H,ArH ) · 7.83 -7.72 ( m > 2H > ArH ) , 7_00 ( m, 1H,ArH ) , 6.92 ( m,1H,

ArH), 5.02 (m, 1H, CH), 1 94 (d, 1H, J = 3 · 8 Hz, -OH), 1.58 (d, 3H, -CH3). <Synthesis of oxime complex compound A> Q In a Dimrod cooling tube and a two-necked flask having a three-way valve, the above compound (W) (28 8 mg '0.2 mmol), potassium carbonate ( 138 mg '1.0 mmol), compound (A2) (118 mg, 0.5 mmol), and replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and the mixture was stirred for 4 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and after adding chloroform, the insoluble matter was removed by filtration with fluorite. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 2/8 to chloroform, gradient), and then methanol/dichloromethane. Recrystallization -38 - 200925242 Crystals, dried under vacuum to obtain an orange solid polymerizable ruthenium compound (A). The yield was 37 mg and the yield was 1%. The result of the identification of the compound (A) is shown below. !H-NMR ( 270MHz > CDC1 3 ) ppm : 8 · 3 1 ( m , 2H, ArH ) , 8.23 (dd * 1H,] [=8 · 6,2 ·' 6Hz, ArH ) , 7.70 (d, 1H, J = 8. 9Hz, ArH), 7.34 ( m , 3H , ArH) -6.99 (dd , 1H, J = 5.9, 1.9Hz , ArH ) , 6.93 ( dd , 1H , J = 5.9 , 1.9Hz , ArH ), 6.44 -6.25 ( m , 7H, ArH + -CH=CH2) , 5 • 47 ( d > 1H, J = 17.8Hz , -CH=CH2) , 5.22 (d, 1H, J = 10.8Hz, - CH = CH2 ) , 1.3 5 ( s, 9H,

-C(CH3)3), 1.34 (s,9H,-C(CH3)3). FAB-MS: 901 (M+). ' Elemental analysis Calcd for C43H36F6IrN3: C, 57.32; Η, 4.03; F, 12.65; Ir, 21.33; N, 4.66. Found : C,57.44 ; H, 3.99 ; N , 4.58 .合成 [Synthesis Example 2] Synthesis of polymerizable ruthenium complex compound (B) -39- 200925242 [Chem. 18]

(B1) (B2)

(B5)

(W) (B)

The description will be made with reference to the above flow. ❿ <Synthesis of Compound (B1)> In an eggplant-shaped flask, 4-amino-2-chloropyridine (22.08 g, 172 mmol) and N,N-dimethylamine oxime ratio (420 mg) were added. 3.44 mmol), and acetic anhydride (35.07 g, 343 mmol), and stirred at 70 ° C for 2 hours to react. After the reaction, the mixture was cooled to room temperature, and methanol (20 ml) was carefully added while being cooled, and further purified water (70 ml) was added to crystallize. The crystals were collected by filtration, washed with pure water, and dried in vacuo to give a colorless crystal compound (B1). The yield was 2 9.2 0 g and the yield was 100%. -40- 200925242 The identification result of the compound (B 1 ) is shown below. i-NMR ( 270MHz, CDC13 ) ppm : 8.26 ( d ' 1H, J = 5.7Hz, ArH) , 7 · 62 ( d,1H, J = 1.6Hz, ArH ) , 7.47 (br,1H,NH ) ,7.34 ( dd, 1H, J = 5.5, 2_0Hz,

ArH), 2.23 (s, 3H, CH3). <Synthesis of Compound (B2)> 0 In the Dimrod's cooling tube and a three-necked flask having a three-way valve, the above compound (B1) (1.71 g, 10.0 mmol), 2,4-difluorobenzene was added. Boronic acid ( 1.895 g, 12.0 mmol), sodium carbonate (2.12 g, 20.0 mmol), 1,2-dimethoxyethane (30 ml), and pure water (1 〇 ml) were purged with nitrogen. Further, [1, fluorene-bis(diphenylphosphino) 'ferrocene-dichloropalladium(Π) dichloromethane complex (163 mg, 0.2 mmol) was added, and the mixture was stirred for 4 hours and refluxed to cause a reaction. . After the reaction, the mixture was cooled to room temperature, and ethyl acetate was added and then washed with aqueous sodium chloride. After the organic layer of the obtained Q was dried over magnesium sulfate, the mixture was filtered and evaporated. The residue was purified by hydrazine gel column chromatography (solvent: ethyl acetate / chloroform = hexane / 1 - I / O, gradient), the solvent was evaporated, and dried under reduced pressure to give a white solid. Compound (B2). The yield was 2.10 g and the yield was 85 %. The result of the identification of the compound (B2) is shown below. !H-NMR ( 270MHz » CDC13 ) ppm : 8.59 ( d,1H, J = 5.7Hz,ArH) , 8.00 ( m,1H,ArH ) ,7.73 ( s,1H,

ArH ) , 7.64 ( dd, 1H, J = 5.7, 1.9 Hz, ArH) · 7.37 (br, 1H, NH ) , 6 · 99 ( m, 1H, ArH ) , 6.91 ( m, -41 - 200925242 1H, ArH ), 2.24 ( s, 3H, CH3 ). <Synthesis of Compound (B3)> In the eggplant-shaped flask, the compound (B2) (2.1 mmol) and 10% hydrochloric acid (30 g) were added, and the mixture was stirred for 3 hours to cause a reaction. After the reaction, the reaction solution is filtered with glass fiber in a hot state to remove insoluble matter, and when the filtrate is cooled, there is a hydrochloride salt tt Q. The filtrate of the precipitated hydrochloride is neutralized by adding sodium hydroxide to extract the organic matter. . After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated to give Compound (B3) as a colorless liquid. Production g ° ' < Synthesis of Compound (B4 )> In the eggplant flask, compound (B3) (1.79 aqueous hydrogen bromide (40 ml), pure water (40 ml) and bromine (23 mg > 0.16 mmol), stirred at 60 ° C. In a 1 aqueous solution of sodium nitrite (5 ml, 25 mmol), and then mixed for another 30 minutes to cause the reaction, after the reaction, the addition of the hydrazine hydroxide to become alkaline, It will be a gray solid precipitate. Filter the solid and wash it with pure water, dissolve it in ethyl acetate, remove the insoluble matter, distill off the solvent, recrystallize from methanol/water, and dry in vacuum. The colorless crystalline compound (B4) was 1.55 g. The yield of the compound (B2) was 68%. The compound identification results are as follows: 0 g ' 8.46 [Reflow occurred I filter paper was over. Filtered with chloroform. The amount is 1.79 g) '30% copper (I) is added with 5N 6 ° ° C under stirring), when the reaction [the gray ruthenium membrane filter crystal. Sprinkle. The yield is 丨(B4)-42-200925242 'H-NMR ( 270MHz * CDC13 ) ppm : 8.52 ( d ' 1H, J = 5.4Hz > ArH ) , 8.01 ( m,1H,Ar H ) , 7.95 ( s , 1H,

ArH), 7.44 (dd, 1H, J = 5.1, 1.6 Hz, ArH), 7.01 (m, 1H, ArH), 6 · 9 3 (m, 1H, ArH). <Synthesis of Compound (B5)> In a Dimrod cooling tube and a three-necked flask having a three-way valve, a compound (B4) (540 mg '2.0 mmol), sodium carbonate (424 mg, 4.0) was added. Methyl), 1,2-dimethoxyethane (6 ml) ' and pure water (2 ml), and purged with nitrogen. Further, dibutyl borohydride (529 / zl, 2.4 mmol) and tetrakis(triphenylphosphine)palladium (163 mg, 0.2 mmol) were added, and the mixture was stirred for 2.5 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature. After ethyl acetate was added, the organic layer was washed with aqueous sodium chloride. The obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform / hexane = EtOAc = EtOAc). B5). The yield was 3 88 mg and the yield was 89%. The result of the identification of the compound (B5) is shown below. !H-NMR ( 270MHz « CDC13 ) ppm : 8.65 ( d,1H, J = 5.4Hz,ArH ) ,7 · 9 8 ( m,1H,Ar H ) ,7.72 ( s,1H,

ArH ) , 7.26 ( dd, 1H, over wrapped w/ chloroform, ArH ) , 7.00 ( m, 1H, ArH ) , 6 · 92 ( m, 1 H, ArH ), 6.73 ( dd, 1H, J = 1 7 · 8,1 0 · 8 Hz, - CH = CH2 ) ,6 · 02 ( d, 1H, J=1 7_6Hz, -CH = CH2 ) , 5.22 ( d,1H, J=l〇.8Hz, -43- 200925242 -ch=ch2). <Synthesis of oxime complex compound (B)> The above compound (W) (288 mg, 0.2 mmol) and potassium carbonate were added to a Dimrod cooling tube and a two-necked flask equipped with a three-way valve. 138 mg '1.0 mmol) and replaced with nitrogen. Further, mesitylene (4 ml), compound (B5) (109 mg' 0.5 mmol), and trifluoromethane (I) (123 mg, 0.48 mmol) were added, and the mixture was stirred for 3 hours and refluxed. react. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, followed by filtration with fluorite to remove insolubles. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography. Since the separation was incomplete, the HPLC was separated (column: Shodex 5C8 20E, eluent: THF/. water = 7/3, flow rate: 3 ml/min) for separation. Recrystallization from methanol/dichloromethane was carried out under vacuum to give a yellow solid polymerizable compound (B). The yield was 1 13 mg and the yield was 31%. The results of the identification of the compound ❹ (B) are shown below. iH-NMR ( 270MHz, CDC13 ) ppm : 8_3 1 ( s, 2H, ArH ), 8.25 ( s ' 1Η ' ArH ) , 7.39 ( d,1H, J = 5.9Hz, ArH ), 7.37 ( d,1H ' J = 5.9 Hz, ArH ) , 7.32 ( d, 1H, J = 6.2 Hz, ArH ) ' 6 · 94 ( m, 3 H, ArH ) , 6_70 ( dd , 1H, J = 17.4, l〇.9Hz, -CH = CH2 ) , 6.39 ( m,3H >

ArH ) ' 6.27 ( m ' 3H > ArH ) , 5.97 ( d,1H, J=17.3Hz ' -CH = CH2 ) , 5.51 ( d,1 H,J = 1 0 · 5 H z,- CH = CH2 ), 1.34 ( s ' 9H, -C(CH3)3) , 1_34 ( s, 9H, -44 - 200925242 -c(ch3)3). FAB-MS: 901 ( M+ ). Elemental analysis Calcd for C43H36F6IrN3: C, 57.32; Η, 4.03; F, 12.65; Ir, 21.33; N, 4.66. Found : C,57.51 ; H, 4.00 ; N , 4.73 . [Synthesis Example 3]

Synthesis of polymerizable ruthenium complex compound (C) [Chem. 19]

NaN02 h2so4

(C1) (C2)

The description will be made with reference to the above flow. <Synthesis of Compound (C1)> In an eggplant-shaped flask, 40% sulfuric acid (50 g) and 4-amino-2-chloro-45-200925242 pyridine (3.0 g, 23.3 mmol) were added to dissolve. After stirring at 0 ° C, sodium nitrite (1.93 g, 28.0 mmol) was added, and the mixture was stirred at room temperature for 24 hours to cause a reaction. After the reaction, the reaction solution was neutralized by adding an aqueous sodium hydroxide solution and an aqueous sodium hydrogencarbonate solution, and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated to dryness, and then evaporated to dryness to dryness to dryness to give the product as a brown solid as 2-chloro-4-hydroxypyridine (compound (C1)). The yield was 2.78 g and the yield was 92%. The identification results of the compound Q (C1) are shown below. W-NMR ( 270MHz, DMSO-d6) ppm : 11.20 ( s, 1H, -OH ), 8.09 (d, 1H, J = 5.4Hz, ArH ) , 6.81 ( s, 1H,

ArH), 6.77 (d, 1H, J = 2.2 Hz, ArH). * <Synthesis of Compound (C2)> Compound (C1) (667 mg, 5.15 mmol) and potassium carbonate (1.424 〇g &gt) were added to a Dimrod cooling tube and a two-necked flask equipped with a three-way valve. ; 10.3 mmol ), and 3,5-di-tert-butylbutyl-4-hydroxytoluene (3 mg), and replaced with nitrogen. Further, dehydrated DMF (20 ml) and 4-vinylbenzyl chloride (1.179 g, 7.73 mmol) were added, and the mixture was stirred at 80 ° C for 2 hours to cause a reaction. After the reaction, chloroform was added, and the organic layer was washed twice with pure water. The obtained organic layer was dried over magnesium sulfate, and then filtered and evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 1/1 to chloroform, gradient), and the solvent was evaporated. ). The yield was 1.247 g and the yield was 99%. The identification result of the compound (C2) is shown in the following -46 - 200925242. iH-NMR ( 270MHz, CDC13 ) ppm : 8.20 ( d,1H, J = 5.4Hz, ArH ) , 7.45 ( d - 2H, J = 7.8Hz > ArH ) , 7.3 5 (d, 2H, J = 8.4Hz > ArH ) , 6.9 1 ( d,1H, J = 2.2Hz >

ArH ) , 6.81 ( dd, 1H, J = 5.9, 2.4 Hz, ArH ) > 6.73 (dd, 1H, Bu 17.8, 10.8 Hz, -CH = CH2 ), 5.78 (d, 1H, J = 17.6 Hz, - CH = CH2), 5.29 (d, 1H, J = 11.3 Hz, ❹ -CH = CH2), 5.09 (s, 2H, -CH20-). <Synthesis of Compound (C3)> In a Dimrod cooling tube and a three-necked flask having a three-way valve, a compound (C2) (1240 g, 5.05 mmol) and 2,4-difluorophenylboronic acid were added. (956 mg, 6.06 mmol), sodium carbonate (1.071 g, 10.1 mmol), 1,2-dimethoxyethane (15 ml), and pure water (5 ml) were purged with nitrogen. Further, tetrakis(triphenylphosphine)palladium(0) (116 Q mg '0.1 mmol) was added, and the mixture was stirred for 3 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and after adding pure water, the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 1/1 to chloroform to ethyl acetate/chloroform = 1/9, gradient), and the solvent was evaporated. The compound (C3) which is a colorless liquid is obtained by drying. The yield was 3 89 mg and the yield was 24%. The result of the identification of the compound (C3) is shown below. h-NMR ( 270MHz , CDC13 ) ppm : 8.52 ( d , 1H , -47- 200925242 J = 5.7Hz > ArH ) , 7_ 99 ( m,1H,ArH ) , 7.45 ( d,2H, J = 8.6Hz, ArH ) , 7.40 ( d, 2H, J = 8 · 1 Hz, ArH ) > 7.36 (m, 1H, ArH ) , 7 · 0 2- 6 · 8 3 ( m, 3 H, ArH ) , 6.73 (dd , 1H, J=17_4, 10_9Hz, -CH = CH2), 5_78 (d, 1H,

J = 1 7.8 Hz, -CH = CH2), 5.28 (d, 1H, J = ll.lHz, -CH = CH2) 5. 1 5 (s, 2H, -CH2〇-). 0 <Synthesis of Polymerizable Complex Compound (C)> The above compound (W) (28 8 mg ' 0.2 mmol ) was added to a Dimrod cooling tube and a two-necked flask equipped with a three-way valve. Potassium carbonate (138 mg, 1.0 mmol), compound (C3) (162 mg, 0.5 mmol), and 3,5-ditributylbutyl-4-hydroxytoluene (3 mg) were replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and the mixture was stirred for 3 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, followed by filtration with fluorite to remove hydrazine insoluble matter. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 2/8 to chloroform, gradient), and recrystallized from methanol/dichloromethane. After drying in vacuo, a yellow microcrystalline polymerizable ruthenium complex compound (C) was obtained. The yield was 8 7 mg and the yield was 22%. The results of the identification of the compound (C) are shown below. 1H-NMR ( 270MHz ' CDC13 ) ppm : 8.30 ( m, 2H,

ArH ) ' 7.90 ( m ' 1H,ArH ) ,7.4 5 ( d,2 H,J = 8 · 4 Hz, ArH ) ' 7.40-7.3 7 ( m,3H,ArH ) , 7.30 ( d,1H, J= 5.7 Hz, ArH ) , 7 _ 2 3 ( d, 1H, J = 6 · 5 Hz, ArH ) , 6.93 -48- 200925242 (d, 2H, J = 5.9Hz, ArH ) , 6.73 ( dd, 1H, J = 17.6, 10.8 Hz, -CH = CH2), 6.5 1 ( dd, 1H, J = 6.2, 2.7 Hz >

ArH ) , 6.38 ( m, 3H, ArH ) , 6 · 3 0 - 6 · 2 4 ( m, 3 H,

ArH ) , 5.78 ( d,1H, J=17.8Hz, -CH = CH2 ) , 5.29 ( d, 1H, J=1 0.8Hz, -CH-CH2 ) , 5.13 ( s, 2H, -CH2〇-), 1.34 ( s, 9H, -C(CH3)3 ) > 1 .33 ( s > 9H > -C(CH3)3 ). FAB-MS: 1 007 ( M+ ). 0 Elemental analysis Calcd for C5〇H42F6IrN3〇: C,5 9.6 3 ; H, 4.20; F, 11.32; Ir, 19.09; N, 4.17; O, 1.59. Found : C, 5 9.8 5 ; H, 4.12; N, 4.20. [Synthesis Example 4] 'Synthesis of a polymerizable ruthenium complex compound (D) [Chem. 20]

(D1) (D2)

(W) (D) Refer to the above procedure for explanation. <Synthesis of Compound (D1)> -49- 200925242 In a two-necked flask having a three-way valve and a dropping funnel, methyltriphenylsulfonium bromide (4.29 g, 12 mmol) was added and replaced with nitrogen. . After further adding dehydrated THF (100 ml), the mixture was cooled in an ice bath, and a 1.6 Μ η-butyllithium hexane solution (7.5 ml, 12 mmol) was gradually added from the dropping funnel, and the mixture was placed at 〇 ° C. Stir for 2 hours. Furthermore, 3-bromo-2,4-difluorobenzaldehyde (2.21 g, 10 mmol) synthesized according to the method described in International Publication No. WO09935117 was added, and the mixture was stirred at room temperature for 0 to night to cause a reaction. After the reaction, pure water was carefully added and the reaction product was extracted with chloroform. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 1/4 to 1/1, gradient), and then the solvent was evaporated and dried under reduced pressure to give a colorless liquid compound. (D1). The yield was 1.58 g and the yield was '72%. <Synthesis of Compound (D2)> In a Dimrod cooling tube and a two-necked flask having a three-way valve, Compound (D1) (1.58 g '7.2 mmol), lithium chloride (916 mg') was added. 21.6 mmol), replaced with nitrogen. Further adding dehydrated 1,4 -dioxane (15 ml), 2-(tributyltin)pyridine (2.91 g, 7.9 mmol), tetrakis(triphenylphosphine)palladium (〇) (231 mg, 0.2 mmol), and 3,5-Di-tert-butylbutyl-4-hydroxytoluene (5 mg) was refluxed and stirred for 2 hours to cause a reaction. After the reaction, a 10% aqueous solution of potassium fluoride and ethyl acetate were further added, and the mixture was stirred at room temperature for 1 hour, and then the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered over Celite <~> The residue was purified by hydrazine gel column chromatography (solvent: chloroform / hexane = 1 / 1 to chloroform), and the solvent was evaporated to dryness to dryness to afford compound (D2) as colorless liquid. The yield was 1.22 g and the yield was 78%. Synthesis of polymerizable ruthenium complex compound (D) In a Dimrod cooling tube and a two-necked flask having a three-way valve, φ was added to the above compound (W) (288 mg, 0.2 mmol), potassium carbonate ( 138 mg '1.0 mmol), compound (D2) (109 mg, 0.5 mm 〇l), and 3,5-ditributyl -4- 4 hydroxytoluene (3 mg) were replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0-48 mmol) were added, and the mixture was stirred for 4 hours and refluxed to cause a reaction. • After the reaction, it was cooled to room temperature, and chloroform was added thereto, followed by filtration with fluorite to remove insoluble matter. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 2/8 to chloroform, gradient), and recrystallized from methanol/dichloromethane. After drying in a vacuum, a yellow microcrystalline polymerizable ruthenium complex compound (D) was obtained. The yield is 1〇1 mg and the yield is 28%. The result of the identification of the compound (D) is shown below. FAB-MS: 90 1 ( M+ ). Elemental analysis Calcd for C43H36F6IrN3: C, 57.32; Η, 4.03; F, 1 2.6 5 ; I r, 2 1 . 3 3 ; N, 4.6 6. F o u n d : C, 5 7 · 3 7 ; Η, 4.19 ; N , 4_65 . [Synthesis Example 5] -51 - 200925242 Synthesis of polymerizable ruthenium complex compound (E) [Chem. 21] d"

Fy_^0H k2co5 Br-〇~F

The description will be made with reference to the above flow. (E1) <^-SnBus PdiPPha)*, UCI l,4>dloxar>« (E2) <Synthesis of Compound (El)> In Dimrod's cooling tube and with three-way valve and dropping funnel In the flask, 3-bromo-2,4-difluorophenol (2.09 g, 10 mmol), potassium (2.76 g' 20 mmol), and 3,5- synthesized as described in the International Publication No. WO09935 1-17 were added. Di-tert-butyl-4-hydroxyl (3 mg) was replaced with nitrogen. Further adding dehydrated DMF (40

And 4-B-sodium chloride (2.29 g, 15 mmol) was mixed at 80 ° C for 2 hours to react. After the reaction, chloroform was added and washed with pure water. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated to dissolve. The residue was purified by gel column chromatography (solvent: chloroform / 1/1 to chloroform, gradient). Under a reduced pressure, dry-52-two-port method toluene (ml). Institute = Dry and 200925242 A compound (El) of white solid was obtained. The yield was 3.12 g and the yield was 舄 9 6%. <Synthesis of Compound (E2)> Compound (E1) (1.63 g, 5 mmol) and lithium chloride (636 mg, 15) were added to a Dimrod cooling tube and a two-necked flask equipped with a three-way valve. Mmmol), replaced by nitrogen. Further added dehydrated 1,4-dioxane oxime (10 ml), 2-(tributyltin) B ratio steep (2.02 g' 5.5 mmol), tetrakis(triphenylphosphine)palladium (ο) (116 mg, 0.1 rnmol) And 3,5-di-tert-butylbutyl-4-hydroxytoluene (3 mg) were refluxed and stirred for 2 hours to cause a reaction. After the reaction, an aqueous solution of 1% by weight of potassium fluoride and ethyl acetate were further added, and the mixture was stirred at room temperature for 1 hour and then extracted with ethyl acetate. The organic layer obtained was dried over magnesium sulfate, filtered, and the solvent was evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 1/1 to chloroform), and then the solvent was evaporated and dried under reduced pressure to give a white solid compound (E2). ). The yield was 1.12 g and the yield was 69%. <Synthesis of Polymerizable Complex Compound (E)> The above compound (W) (28 8 mg '0.2 mmol ) was added to a Dimrod cooling tube and a two-necked flask equipped with a three-way valve. Potassium carbonate (138 mg '1.0 mmol), compound (D2) (109 mg '0.5 mmol), and 3,5-ditributylbutyl-4-hydroxytoluene (3 mg) were replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and the mixture was stirred for 4 hours and refluxed to cause a reaction. -53- 200925242 After the reaction, the mixture was cooled to room temperature, and then added with chloroform, and then filtered over Florite. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography (solvent: chloroform / hexane == 2/8 chloroform, gradient) and purified by methanol/dichloromethane. After drying, a polymerizable ruthenium complex compound (E) of yellow crystals is obtained. The yield of 113 mg is 28%. The result of the identification of the compound (E) is shown below. FAB-MS: 1 007 ( M+ ). ❹ 兀 分析 Calcd for C5 〇 H42F6IrN3 (): C, 59.63; Η, 4. F, 11.32; Ir, 19.09; N, 4.17; 0, 1.59. Found : 59.80 ; H,4_09 ; N,4.31. [Synthesis Example 6] Synthesis of polymerizable ruthenium complex compound (F) Removal of layering, coloration, yield 20; C,

-54- 200925242 [Chem. 22]

(H〇) 2B

Ο-

Pd (PPh Mountain, NajQOa

(W21) DME, H20

PdiPPha)* Na2C03

〇Hc^a (F1)

The description will be made with reference to the above flow. <Synthesis of Compound (W21)> Burning 2-chloro-4-methyl H in a Dimrod cooling tube and a three-way valve with a three-way valve (1.276 g, 10.0 mmol), 4-acid (1.679 g, 12.0 mmol), potassium carbonate (2.12 mmol), 1,2-dimethoxyethane (3〇1111), and East bottle, fluorophenyl boron g, 20.0 e water (ίο -55 - 200925242 ml) 'And breathe with nitrogen. Further, tetrakis(triphenylphosphine)palladium (ruthenium) (23 1 mg '0.2 mmol) was added, and the mixture was stirred for 2 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and after adding chloroform, the organic layer was washed with aqueous sodium chloride. The obtained organic layer was dried over magnesium sulfate, and then filtered and evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform / hexane = 1 / 1 - chloroform, gradient), and the solvent was evaporated, and dried under reduced pressure to give a colorless liquid compound (W21) ). The yield Q was 1.52 g, and the yield was 81% » <Synthesis of Compound (W)> In a Dimrod's cooling tube and a 50 ml two-necked flask with a three-way valve, Add compound (W21) (449 mg' 2.4 mmol), ruthenium (III) chloride trihydrate (353 mg, 1 mmol), 2-ethoxyethanol (15 ml), pure water (5 ml), After the obtained solution was purged with nitrogen for 5 minutes, it was stirred under nitrogen for 15 hours and refluxed to carry out a reaction. After the Q reaction, it was cooled to room temperature, and 30 ml of pure water was added to precipitate a product. The precipitate was filtered, washed with 50 ml of a mixed solution of methanol/water = 7/3, and dried under reduced pressure to give a yellow powder compound (W2). The yield was 504 m g and the yield was 84%. This powder was used without identification and was used directly in the following procedure. <Synthesis of Compound (F1)> 'Addition of 6-chloropyridine-3-carbaldehyde (1.416 g, 10.0 mmol), 4-fluorobenzene in a Dimrod's cooling tube and a three-necked flask with a three-way valve Boron-56- 200925242 acid (1.679 g, 12.0 mmol), sodium carbonate (2.12 g, 2 0 · 0 mmol), 1,2-dimethoxy hospital (30 ml), and pure water (l〇ml ), pumping with nitrogen. Further, tetrakis(triphenylphosphine)palladium (ruthenium) (231 mg '0.2 mmol) was added, and the mixture was stirred for 2 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and after adding chloroform, the organic layer was washed with a sodium chloride aqueous solution. The obtained organic layer was dried over magnesium sulfate, and then filtered and evaporated. The residue was purified by hydrazine gel column chromatography (dissolved H solution: chloroform / hexane = 1 / chloroform, gradient), and the solvent was evaporated to dryness to give a white solid compound (F1). ). The yield was 1.520 g - the yield was 81%. <Synthesis of Compound (F2)> 'In an eggplant-shaped flask having a three-way valve, Compound (F1) (402 mg '2.0 mmol) was added and replaced with nitrogen. Further, after dehydrating THF (4 ml) was added, 3M methylmagnesium bromide diethyl ether solution Q (0.73 ml > 2.2 mmol) was slowly added thereto, and the mixture was stirred at room temperature for 4 Torr to react. After the reaction, pure water was carefully added and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was evaporated. The residue was purified by hydrazine gel column chromatography (solvent: chloroform - ethyl acetate / chloroform = 2/8, gradient), and the solvent was evaporated, and dried under reduced pressure to give a colorless liquid compound ( F2). The yield was 40 8 mg and the yield was 94%. <Synthesis of Polymerizable Complex Compound (F)> -57- 200925242 Into a Dimrod cooling tube and a two-necked flask having a three-way valve, the above compound (W2) (240 mg '0.2 mmol) ), carbon (13 8 mg '1.0 mmol), compound (F2) (109 mg mmol), and replaced with nitrogen. Further, mesitylene (4 ml) of silver (I) fluoromethanesulfonate (123 mg, 0.48 mmol) was added, and the mixture was stirred and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and after adding, it was filtered through a fluorite to remove insolubles. The solvent of the filtrate was distilled off, and the residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = chloroform, gradient), and then crystallized from methanol/dichloromethane. Polymeric oxime complexation (F) of a color solid. The yield was 51 mg and the yield was 33%. The results of the compound (F) are shown below. FAB-MS: 763 ( M+ ). Elemental analysis Calcd for C37H27F3IrN3: C, 58.26; Η, 3 F, 7.47; Ir, 25.20; N, 5.51. Found : C,58.20 ; Q 3.65 ; N , 5.46 . [Synthesis Example 7] <Synthesis of other polymerizable ruthenium complex compound> The polymerizable ruthenium complex compound shown below was synthesized by the method of the above polymerizable ruthenium complex compounds (A) to (F). Compound ((T)., potassium acid addition, 0.5 and tri- 4 small chloroform and 2/8~ recombination of 57; Η, synthesis G) - -58- 200925242

59- 200925242

[Synthesis Example 8] Synthesis of polymerizable ruthenium complex compound (U) Ο ¥ [Chem. 25]

(U1

(W)

G

Ph3PCH3, n-BuLi THF (U) is described with reference to the above scheme. <Synthesis of ruthenium complex compound (u 1 )> In a Dimrod cooling tube and a two-necked flask having a three-way valve, the above compound (W) (288 mg, 0.4 mmol) (576 mg, 0.4 mmol), potassium carbonate (276 mg, 2.0 mmol), and 4-(2-la-p-styl)benzaldehyde (183 mg, 1·〇mmol), and replaced with nitrogen. Further, after adding mesitylene (8 ml) and silver (I) trifluoromethanesulfonate (247 mg, 0.996 mmol), they were stirred for 3 hours and refluxed to cause a reaction. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, followed by filtration with fluorite to remove insolubles. The solvent of the filtrate was distilled off, and the residue was purified by a ruthenium gel column chromatography (solvent: chloroform chloroform), and recrystallized from methanol/dichloromethane, and dried under vacuum to obtain a yellow crystal. A chelating complex compound (U 1 ). The yield was 2 1 5 mg and the yield was 31%. <Synthesis of Polymerizable Complex Compound (U)> The methyltriphenyl bromide (120 mg, 0.34 mmol) was dissolved in 10 ml of THF, and 1.6 η of η was added at 0 °C. Butyl lithium hexane solution (0.18 mg > 0.29 mmol). After stirring at 〇 ° C for 30 minutes, the hydrazine compound (U1) (208 mg, 0.24 mmol) was added, and the mixture was stirred at room temperature for 2 hours to cause a reaction. After the reaction, dilute hydrochloric acid was added to the reaction mixture, and the organic matter was extracted with chloroform. After the obtained organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure. The residue was purified by hydrazine gel column chromatography (solvent: chloroform/hexane = 3/1), and then recrystallized from methanol/dichloromethane to obtain a yellow crystalline polymerizable ruthenium complex. Compound (U). The yield was 105 mg and the yield was 51%. The results of the identification of the compound (U) are as follows. FAB-MS: 865 ( M+ ). -61 - 200925242 Elemental analysis Calcd for C43H38F4IrN3: C, 59.71; Η, 4.43; F, 8.79; Ir, 22.22; N, 4.86. Found : C , 59.30 ; Η , 4.40 ; N , 4.92 . [Example 1] Synthesis of a polymerizable ruthenium complex compound and a copolymer of a polymerizable compound (X) and a polymerizable compound (Y) 〇 In a closed container, 'the polymerizable ruthenium complex synthesized in the above Synthesis Example 1 was added' 100 mg of the compound (A) and the following polymerizable compound (X) (same as the above polymerizable compound (E02)): 450 mg and the following polymerizable compound (Y) (same as the above polymerizable compound (E19)) 450 mg, add dehydrated toluene (9.9 ml), then add the free radical polymerization 'starter dimethyl 2,2'-azobis(2-methylpropionate) (trade name V-601 ( The toluene solution (0.1 M, 198 " 1) of Wako Pure Chemical Industries Co., Ltd.) was repeated five times for the freeze degassing operation. The mixture was closed in a vacuum and stirred at 60 ° C for 60 hours to cause a reaction. After the reaction, the reaction was dropped into acetone (500 ml) to cause precipitation. Further, the reprecipitation purification of toluene-acetone was repeated twice and purified, and then dried overnight at 50 ° C to obtain the intended copolymer (P-A ). The copolymerization ratio of the obtained copolymer, the estimated weight average molecular weight (Mw) measured by GPC in terms of polystyrene, the ICP luminescence analysis, and the copolymerization ratio in the copolymer estimated by the result of 13 C-NMR are shown in the table. 1. -62- 200925242

实施 [Examples 2 to 20, Comparative Examples 1 to 3] The same procedure as in Example 1 was carried out except that the polymerizable ruthenium compound (A) was changed to the polymerizable ruthenium complex described in Table 1. The copolymer is synthesized by the method. The copolymers of these were also recorded in the same manner as in Example 1 to have a recovery ratio, a weight average molecular weight (Mw), and a copolymerization ratio. Further, the 'polymerizable hydrazine compound (V) is synthesized according to the method described in JP-A-2003-206320. © [Chem. 27]

-63- 200925242 [Table i]

Polymeric ruthenium complex compound copolymer recovery [%] Mw xlO-3 copolymerization ratio (% by mass) 铱 complex compound (X) Compound W Example 1 (A) (PA) 85 52 9.7 45.7 44.6 Example 2 (B) (PB) 84 49 10.1 45.2 44.7 Example 3 (C) (PC) 91 67 10.4 44.6 45.0 Example 4 (D) (PD) 83 50 9.1 45.2 45.7 Example 5 (E) (PE) 89 68 10.3 45.0 44.7 Example 6 (F) (PF) 84 62 9.9 45.0 45.1 Example 7 (G) CP-G) 94 81 9.7 44.5 45.8 Example 8 (H) iP-H) 90 43 10.4 45.3 44.3 Example 9 (I) (PI) 88 51 10.1 45.2 44.7 Example 10 (J) (PJ) 88 60 10.2 45.1 44.7 Example 11 (K) (PK) 84 59 10.2 45.2 44.6 Example Π (L) (PL) 81 47 9.7 45.0 45.3 Example 13 (M) (PM) 91 77 10.0 44.9 45.1 Example 14 (N) (PN) 77 39 8.8 46.0 45.2 Example 15 (〇) (PO) 87 69 10.4 45.1 44.5 Example 16 ( P) (PP) 79 41 9.9 45.7 44.4 Example 17 (0) CP-O) 86 53 9.7 45.3 46.0 Example 18 (R) CP-R) 91 57 10.4 44.6 45.0 Example 19 (5) (PS) 93 59 10.3 45.0 45.7 Example 20 (T) (PT) 92 70 10.3 46.0 43.7 Comparison 1 (V) (pv) 81 48 9.9 45.1 45.0 Comparative Example 2 (P) 86 60 — 50.4 49.6 Comparative Example 3 (U) (PU) 85 54 10.0 45.1 44.9 [Example 21] Preparation of organic EL element at 25 mm See one side of the glass substrate on the side, use the attached

An ITO-64-200925242 (indium tin oxide) substrate (Nippo Electric Co., LTD.) of a straight ITO electrode was formed as an anode and a strip of 4 mm to prepare an organic EL device. First, on the ITO (anode) to which the ITO substrate is attached, poly(3,4-extended ethyldioxythiophene)·polystyrenesulfonic acid (manufactured by Bayer, trade name "Betalong") The coating was carried out under the conditions of a spin coating method, a number of revolutions of 3,500 rpm, and a coating time of 40 seconds, and then dried at 60 ° C for 2 hours in a vacuum dryer under reduced pressure to form an anode buffer layer. The resulting anode buffer layer had a film thickness of about 50 nm. Next, a coating solution for forming a light-emitting layer is prepared. That is, 150 mg of the copolymer (PA) synthesized in Example 1 as a light-emitting material was dissolved in chloroform (Special grade manufactured by Wako Pure Chemical Industries, Ltd.), 9850 mg, and the obtained solution was a pore size of 0.2 // m. The filter is filtered to serve as a coating solution. Next, on the anode buffer layer, the prepared coating solution was applied by spin coating, rotation number of 300 rpm, coating time of 30 seconds, and room temperature (2 5 °C) was dried for 30 minutes to form a light-emitting layer.发光 The obtained light-emitting layer has a film thickness of about 10 nm. Next, the substrate on which the light-emitting layer is formed is placed in a vapor deposition apparatus, and the crucible is vapor-deposited to a thickness of 5 nm at a deposition rate of 0.01 nm/s, and then the aluminum as a cathode is vapor-deposited at a rate of 1 nm/s. An organic EL element was fabricated by vapor deposition to a thickness of 150 nm. In addition, the tantalum layer and the aluminum layer are formed in a straight strip shape with two widths and a width of 3 mm with respect to the extending direction of the anode, and four organic light-emitting elements of 4 mm long and 3 mm wide are fabricated for each glass substrate. . Evaluation of EL Characteristics-65- 200925242 Using the "Protagara Blu" DC voltage/current source TR6143 manufactured by "Adelantes", applying voltage to the organic EL element, causing it to emit light, and then use it. The brightness meter BM-8 made by "Tupcon" measures the brightness of the light. The luminescent color obtained by the results, the uniformity of luminescence, the external quantum efficiency at the time of lighting at 100 cd/m2, and the halving time at the time of constant current driving at an initial luminance of 100 cd/rn2 are shown in Table 2. Medium (the external quantum efficiency and the halving time of the luminance are the average 値 of the four elements of the φ formed on one substrate). Further, the measurement result of the luminance halving time in Table 2 is expressed by the relative 値 when the measurement 値 of the element 3 described later is 100. [Examples 22 to 40 and Comparative Examples 4 and 6] The components were produced in the same manner as in Example 6 except that the copolymer (PA) as a light-emitting material was changed to the light-emitting material (copolymer) described in Table 2 . The ELS luminescence characteristics were evaluated in the same manner as in Example 21 for these elements. The results are shown in Table 2. [Comparative Example 5] A component was produced in the same manner as in Example 21 except that the copolymer (PA) as a light-emitting material was changed to a mixture of copolymer (P) 135 mg and ruthenium complex (Z) 15 tng. . The EL light-emitting characteristics were also evaluated in the same manner as in Example 21 for this device. The results are shown in Table 2. -66- 200925242

[化 28]

Luminescent material luminescent color external quantum efficiency "%1 most 売度[cd/m2l luminance halving time Example 21 CP-A) Blue 6.2 31000 213 Example 22 CP-B) Blue 7.3 29000 252 Example 23 CP -C) Blue 7.0 33000 297 Example 24 (PD) Blue 5.9 28000 168 Example 25 (PE) Blue 5.5 27000 180 Example 26 (PF) Blue 6.5 32000 204 Example 27 (PG) Blue 7.5 29000 219 Example 28 (PH) Blue 6.3 33000 199 Example 29 (PI) Blue 6.2 33000 187 Example 30 CP-J) Blue 6.6 29000 192 Example 31 (PK) Blue 6.9 27000 209 Example 32 (PL) Blue 7.1 28000 250 Example 33 (PM) Blue 7.0 31000 243 Example 34 (PN) Blue 5.1 21000 139 Example 35 (P-0) Blue 6.4 26000 180 Example 36 (PP) Blue Color 5.5 20000 167 Example 37 (P-0) Blue 6.5 29000 188 Example 38 (PR) Blue 7.7 32000 192 Example 39 (PS) Blue 5.8 29000 198 Example 40 (PT) Blue 6.6 29000 201 Comparative Example 4 (PV) Blue 6.1 14000 100 Comparative Example 5 (P) + (Z) Blue 5.4 12000 115 Comparative Example 6 (PU) Blue-green 7. 2 34000 281 -67- 200925242 From Table 2, an organic EL element (Examples 2 to 40) using the polymer light-emitting material of the present invention is clearly known, which is conventionally used with a picopyridine acid coordination An organic EL device of a polymer light-emitting material in which a polymerizable ruthenium complex is copolymerized (Comparative Example 4) or an organic EL element in which a ruthenium complex is not copolymerized and simply dispersed in a polymer; In the case of the cattle (Comparative Example 5), it was apparent that the luminous efficiency was high, the life was high, and the highest brightness was also high. In addition, organic EL components, if used:

I a polymer light-emitting material g (Comparative Example 6) obtained by copolymerization of a polymerizable ruthenium complex having no electron-attracting group on a phenylpyridine ligand having a polymerizable substituent, which emits a blue-green color Light. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of an organic EL device of the present invention. [Main component symbol description] © 1 : Substrate 2 : Anode 3 : Hole transport layer 4 : Light-emitting layer 5 = Electron transport layer 6 : Cathode - 68-

Claims (1)

200925242 X. Patent Application Scope 1 - A blue light-emitting polymer compound characterized by a structural unit derived from a compound represented by the following formula (1); (1) [In the formula (1), R1 to R4 and R11 to R are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 to 40. An aralkyl group, an amine group which may be substituted with an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a methyl group which may be substituted with an alkyl group having 1 to 30 carbon atoms, or an electron attracting property The substituent of the electron attracting group may be an alkyl group selected from a halogen atom, a fluorine-substituted carbon number of 1 to 10, a fluorine-substituted carbon number of 1 to 1 (), a cyano group, Aldehyde group, fluorenyl group having a carbon number of 2 to 10, alkoxycarbonyl group having 2 to 1 carbon number, aminocarbonyl group having 1 to 10 carbon atoms, thiocyanate group and sulfonyl group having 1 to 10 carbon atoms At least one of R1 to R4 and at least one of ri!~rm are each independently a substituent of the electron attracting property, and each of R5 to R8 and R15 to R1!! is independently a hydrogen atom. An alkyl group having a carbon number of 3 Å, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 4 carbon atoms, an amine group substituted with an alkyl group having 1 to 30 carbon atoms, and an alkyl group having a carbon number of 丨~" Oxygen, or -69- 200925242 can be substituted with an alkyl group having 1 to 30 carbon atoms Alkyl, but 'R11~R18 in the 1, lines having polymerizable carbon - carbon double bond of the substituent]. 2. The blue light-emitting polymer compound according to claim 1, wherein the electron-attracting substituent is a fluorine atom, a fluorine-substituted alkyl group having 1 to 1 Å, and a fluorine-substituted carbon number. 1~1〇 alkoxy or cyano.蓝色3. The blue light-emitting polymer compound according to claim 1, wherein in the formula (1), R1, R3, R1 1 and R13 are hydrogen atoms, and R2, R4, Ri2 and Rl4 are fluorine atoms. . 4. The blue light-emitting polymer compound according to claim 1, wherein in the formula (1), R1, R3, R4, R11, R13 and R14' are hydrogen atoms, and R2 and R12 are fluorine atoms. 5. The blue light-emitting polymer compound according to any one of claims 1 to 4, further comprising a polymerizable compound which is transportable by a hole and/or a polymerizable compound which is electron transporting. Derived structural unit. An organic electroluminescence device comprising: a substrate; a pair of electrodes formed on the substrate; and an organic layer containing one or more layers of the light-emitting layer between the pair of electrodes; The luminescent layer contains a blue luminescent non-conjugated polymer compound having a structural unit derived from a blue luminescent compound represented by the following formula (1); -70- [Chemical 2] 200925242 (1) [In the formula (1), R1 to R4 and R" are each independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 7 to 40. a base group, an amine group which may be substituted with an alkyl group having 1 to 30 carbon atoms, a carbon number of 1 to 30 alkoxy group, a methyl group which may be substituted with an alkyl group having 1 to 30 carbon atoms, and an electron attracting substituent The electron-attracting substituent may be an alkyl group selected from a halogen atom, a fluorine-substituted carbon number of 1 to 10, a fluorine-substituted carbon number of 1 to 10, a group, an aldehyde group, and a carbon number of 2 to a sulfhydryl group having 10 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfo group having 1 to 10 carbon atoms, at least one of R1 to R4 At least one of R11 to R14 is a substituent which is independently an electron attracting property, and each of R5 to R8 and R15 to R18 is independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, and a carbon number of 6 to 20 An aryl group, an aralkyl group having 7 to 40 carbon atoms, an amine group which may be substituted with an alkyl group of 1 to 30, an alkoxy group having a carbon number of 1 to 30, and an alkyl group having 1 to 30 carbon atoms. Substituted for mercapto, only one of Rn~R18 has a polymeric carbon-carbon double bond substituent]. 7. The organic electroluminescent device according to claim 6, wherein the electron-attracting substituent is a fluorine atom, a fluorine-substituted carbon number of 1 to -71-alkane or a cyanogen, an anthracene each 30 carbon or Take the base of 200925242, a fluorine-substituted alkoxy group having a carbon number of 1 to 10, or a cyano group. The organic electroluminescence device according to claim 6, wherein in the formula (1), 'R丨, R3, R" and R13 are hydrogen atoms, and r2, r4, R12 and R14 are fluorine atoms. 9. The organic electroluminescence device according to claim 6, wherein in the formula (1), R1, R3, R4, R11, R13 and r14 are hydrogen atoms, and R2 and R12 are fluorine atoms. The organic electroluminescence device according to any one of claims 6 to 9, wherein the blue light-emitting non-conjugated polymer compound further contains a polymerizable compound which is transported by a hole and/or A structural unit derived from an electron transporting polymeric compound. A method of producing an organic electroluminescence device, comprising: forming at least one layer of an organic compound layer containing a polymer compound according to any one of claims 1 to 4 on an anode; a step of forming a cathode over the organic compound layer. Ο 12. A method of producing an organic electroluminescence device, comprising: forming at least one layer of an organic compound layer containing a high molecular compound of the fifth aspect of the patent application; and The step of forming a cathode on the organic compound layer. An organic electroluminescence device according to any one of claims 6-9. A picture display device' characterized by having the organic electroluminescence element of claim 10 of the patent application. An organic electroluminescence device according to any one of the above-mentioned items of the present invention. 1 6. A surface-emitting light source characterized by having an organic electroluminescent element according to the first aspect of the patent application. -73-