JP7227789B2 - europium complex - Google Patents

Description

TECHNICAL FIELD The present invention relates to europium complexes having high light resistance.

Optical materials have been actively developed as key materials in the optoelectronics field such as optical communication and displays, and in the energy field such as solar cells. Rare earth metal complexes and the like have been created.

Rare earth metal complexes have the characteristic of absorbing specific wavelengths and emitting light at other wavelengths, and are expected to be excellent wavelength conversion materials. Further, the wavelength conversion material is required to have high light resistance in addition to having strong luminescence.

In recent years, europium complexes having a β-diketonato ligand and a phosphine oxide ligand have been reported as strongly luminescent rare earth metal complexes (see, for example, Patent Documents 1 and 2). In addition, the europium complexes disclosed in Patent Document 3, Patent Document 4, Non-Patent Document 1, Non-Patent Document 2 and Non-Patent Document 3 are similar to the europium complex described in the present application, but regarding the light resistance of these complexes No description.

RUB1453860 JP-A-2003-81986 Japanese Patent No. 2005-223276 Japanese Patent No. 2014-197144

Abstracts of the 36th Inorganic Polymer Research Symposium, The Society of Polymer Science, Japan, 2017, p. 47 The 98th Annual Meeting of the Chemical Society of Japan (2018) Proceedings, The Chemical Society of Japan, 2PA-194 European Journal of Inorganic Chemistry, No. 3, page 639 (2017)

An object of the present invention is to provide a europium complex having high light resistance.

The present inventors have made intensive studies to solve the above problems, and found that a europium complex having a β-diketonato and a phosphine oxide having a specific substituent on the phosphorus atom as a ligand has remarkably high light resistance. The present inventors have found that the present invention has been completed.

That is, the present invention provides a europium complex (Europium complex A) in which only R ¹ has a cyclic alkyl group and a europium complex in which R ¹ and R ² have a cyclic alkyl group (Europium complex B) in the following general formula (1): be.
(i)
General formula (1)

[In the formula, R ¹ is a cyclic alkyl group having 3 to 10 carbon atoms, and R ² and R ³ are phenyl groups represented by the general formula (2a).

(Wherein, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom; a fluorine atom; an alkyl group having 1 to 3 carbon atoms; an alkyloxy group having 1 to 3 carbon atoms; aryloxy group having 6 to 10 carbon atoms; fluoroalkyl group having 1 to 3 carbon atoms; fluoroalkyloxy group having 1 to 3 carbon atoms; or fluorine atom, alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms represents an alkyloxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group, a hydroxyl group, or a phenyl group which may be substituted with a cyano group). However, the case where R ¹ is a cyclohexyl group and R ² and R ³ are phenyl groups is excluded. ^R4 represents a hydrogen atom, a deuterium atom, or a fluorine atom. W ¹ and W ² each independently represent an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group. n represents an integer of 1 to 3; ] A europium complex represented by;
(ii) The europium complex according to (i) above, wherein R ¹ is a cyclohexyl group in general formula (1);
(iii) the europium complex according to (i) or (ii), wherein n is 2 in the general formula (1);
(iv) The europium complex according to any one of (i) to (iii), wherein W ¹ and W ² in the general formula (1) are each independently a fluoroalkyl group having 1 to 6 carbon atoms;
(v) The europium complex according to any one of (i) to (iv) above, wherein R ⁴ is a hydrogen atom in general formula (1);
(vi) In general formula (2a), X ¹ , X ² and X ³ are each independently a hydrogen atom, a methyl group, or general formula (2b)

[In the formula, Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoro It is an alkyl group, a fluoroalkyloxy group having 1 to 3 carbon atoms, or a phenyl group optionally substituted with a fluorine atom. ] and X ⁴ and X ⁵ are each independently a hydrogen atom or a methyl group, the europium complex according to any one of (i) to (v);
(vii)
General formula (1)

[In the formula, R ¹ and R ² are each independently a cyclic alkyl group having 3 to 10 carbon atoms, and R ³ is a cyclic alkyl group having 3 to 10 carbon atoms or a phenyl group represented by general formula (2a).

(Wherein, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom; a fluorine atom; an alkyl group having 1 to 3 carbon atoms; an alkyloxy group having 1 to 3 carbon atoms; aryloxy group having 6 to 10 carbon atoms; fluoroalkyl group having 1 to 3 carbon atoms; fluoroalkyloxy group having 1 to 3 carbon atoms; or fluorine atom, alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms represents an alkyloxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group, a hydroxyl group, or a phenyl group which may be substituted with a cyano group). ^R4 represents a hydrogen atom, a deuterium atom, or a fluorine atom. W ¹ and W ² each independently represent an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group. n represents an integer of 1 to 3; ] A europium complex represented by;
(viii) The europium complex according to (vii) above, wherein R ³ is a cyclic alkyl group having 3 to 10 carbon atoms in general formula (1);
(ix) The europium complex according to (vii) or (viii), wherein R ¹ , R ² and R ³ in the general formula (1) are cyclohexyl groups;
(x) the europium complex according to any one of (vii) to (ix), wherein n is 2 in the general formula (1);
(xi) the europium complex according to any one of (vii) to (x), wherein W ¹ and W ² in the general formula (1) are each independently a fluoroalkyl group having 1 to 6 carbon atoms;
(xii) The europium complex according to any one of (vii) to (xi), wherein R ⁴ is a hydrogen atom in general formula (1);
(xiii) In general formula (2a), X ¹ , X ² and X ³ are each independently a hydrogen atom, a methyl group, or general formula (2b)

[wherein Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, It is an oxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms or a phenyl group optionally substituted with a fluorine atom. ] and X ⁴ and X ⁵ are each independently a hydrogen atom or a methyl group, the europium complex according to any one of (vii) to (xii);
(xiv) The europium complex according to any one of the following formulas (vii) to (xiii), wherein the europium complex is represented by the following formulas 1-1 to 1-11 and 1-19 to 1-21;

It is about.

The present invention will be described in detail below.

R ¹ , R ² , R ³ , R ⁴ , X 1 , X ² , X ³ , X ⁴ , ^{X 5 ,} Z 1 , Z ² , Z ^{3 ,} n, W ¹ and The definition of ^W2 will be explained.

A cyclic alkyl group having 3 to 10 carbon atoms represented by R ¹ in the general formula (1) of the europium complexes A and B of the present invention and R ² and R ³ in the general formula (1) of the europium complex B of the present invention The cyclic alkyl group having 3 to 10 carbon atoms is not particularly limited, but specific examples include cyclohexylmethyl group, cyclopropyl group, 2,3-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2 ,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, bicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-2-yl group, adamantane-2- A cyclic secondary alkyl group such as an yl group, a bicyclo[2.2.1]heptan-2-yl group, an adamantan-1-yl group, and the like can be exemplified. In terms of good light resistance of the europium complexes A and B of the present invention, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecanyl and the like are preferred, and they are particularly inexpensive. is preferably a cyclopentyl group or a cyclohexyl group.

As the alkyl group having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention, linear or branched Although it is not particularly limited, specific examples include methyl group, ethyl group, propyl group and isopropyl group.

The alkyloxy group having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention may be linear or branched may be any alkyloxy group such as methoxy, ethoxy, propoxy and 1-methylethyloxy.

The aryloxy groups having 6 to 10 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention are not particularly limited. but specifically, phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group , 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2, 3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 3,4,5-trimethylphenyl oxy group, 2,3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4-diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3- isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropylphenyloxy group, 2-butylphenyloxy group, 3-butylphenyloxy group, 4-butylphenyloxy group, 2-(1-methylpropyl)phenyloxy group, 3-(1-methylpropyl)phenyloxy group, 4-(1-methylpropyl)phenyloxy group, 2-(2-methylpropyl) ) phenyloxy group, 3-(2-methylpropyl)phenyloxy group, 4-(2-methylpropyl)phenyloxy group, 2-cyclobutylphenyloxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyl An oxy group and the like can be exemplified.

The fluoroalkyl groups having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention may be linear or branched fluoroalkyl group such as trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoro propyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, Examples include 1,1,1,2,3,3,3-hexafluoropropan-2-yl group and 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

The fluoroalkyloxy groups having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention are linear or Any branched fluoroalkyloxy group may be used, and trifluoromethyloxy group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2, 2-difluoroethyloxy group, perfluoropropyloxy group, 2,2,3,3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoro propyloxy group, 1,1-difluoropropyloxy group, 1,1,1,2,3,3,3-hexafluoropropan-2-yloxy group, 2,2,2-trifluoro-1-(trifluoro methyl)ethyloxy group and the like can be exemplified.

When one or more of X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention is a phenyl group, the phenyl group has a fluorine atom and a carbon number substituted with an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group, a hydroxyl group or a cyano group; a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group , a phenyl group substituted with at least one or more of the group consisting of a hydroxyl group and a cyano group (hereinafter also referred to as a "substituted phenyl group"), the substituted phenyl group may be a 2-fluorophenyl group, a 3-fluorophenyl group, 4-fluorophenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 2,4,6-triisopropylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 4-(isopropyloxy ) phenyl group, 2,6-di(isopropyloxy)phenyl group, 2-phenoxyphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl ) phenyl group, 4-(trifluoromethyl)phenyl group, 3,5-bis(trifluoromethyl)phenyl group, 2-(trifluoromethyloxy)phenyl group, 4-(trifluoromethyloxy)phenyl group, 2 '-fluorobiphenyl-2-yl group, 4'-fluorobiphenyl-2-yl group, 4'-fluorobiphenyl-4-yl group, 3',5'-difluorobiphenyl-2-yl group, 2-hydroxyphenyl 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.

The alkyl groups having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include X ¹ , X ² , X ³ , X ⁴ and The same alkyl groups having 1 to 3 carbon atoms as exemplified for X ⁵ can be exemplified.

The alkyloxy groups having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include X ¹ , X ² , X ³ and X ⁴ and the same alkyloxy groups having 1 to 3 carbon atoms as exemplified in the description of X ⁵ can be exemplified.

The aryloxy groups having 6 to 10 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include X ¹ , X ² , X ³ and X ⁴ and the same aryloxy groups having 6 to 10 carbon atoms as exemplified in the description of X ⁵ can be exemplified.

The fluoroalkyl groups having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include X ¹ , X ² , X ³ and X ⁴ and the same fluoroalkyl groups having 1 to 3 carbon atoms as exemplified in the description of X ⁵ can be exemplified.

The fluoroalkyloxy groups having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include X ¹ , X ² , X ³ and X The same fluoroalkyloxy groups having 1 to 3 carbon atoms as exemplified for ⁴ and ^X5 can be exemplified.

Examples of the phenyl group optionally substituted with a fluorine atom represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention include a phenyl group, a 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, perolophenyl group and the like.

As the substituents represented by Z ¹ , Z ² and Z ³ in the general formula (2b) of the europium complexes A and B of the present invention, a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, An isopropyloxy group, a trifluoromethyl group and a trifluoromethyloxy group are preferred.

As the substituents represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) of the europium complexes A and B of the present invention, hydrogen atom, fluorine atom, an alkyl group having 1 to 3 carbon atoms, a methoxy group, an isopropyloxy group, a phenyl group optionally substituted by an alkyl group having 1 to 3 carbon atoms, and an alkyloxy group having 1 to 3 carbon atoms which may be substituted A phenyl group, a phenyl group optionally substituted with a fluorine atom, a phenyl group optionally substituted with a linear fluoroalkyl group, and a phenyl group optionally substituted with a linear fluoroalkyloxy group are preferred, hydrogen atom, methyl group, isopropyl group, methoxy group, isopropyloxy group, 2,6-dimethoxyphenyl group, 2,6-bis(isopropoxy)phenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, A 4-trifluoromethyloxyphenyl group or a phenyl group is more preferred.

As the substituents represented by R ² and R ³ in the general formula (1) of the europium complex A of the present invention, a biphenylyl group optionally substituted with a fluorine atom and having 1 to 3 carbon atoms in terms of good light resistance. A biphenylyl group optionally substituted by a fluoroalkyl group of, a biphenylyl group optionally substituted by a fluoroalkyloxy group having 1 to 3 carbon atoms, a phenyl group optionally substituted by a fluorine atom, a linear fluoro A phenyl group optionally substituted with an alkyl group, a phenyl group optionally substituted with a fluoroalkyloxy group having 1 to 3 carbon atoms are preferable, and a phenyl group, a 2-methylphenyl group, a 2-biphenylyl group, a 3- biphenylyl group, 4-biphenylyl group, 2',6'-dimethoxybiphenyl-2-yl group, 2',6'-bis(isopropoxy)biphenyl-2-yl group, 2',4',6'-tri isopropylbiphenyl-2-yl group, 4'-fluorobiphenyl-2-yl group, 4'-(trifluoromethyl)biphenyl-2-yl group, or 4'-(trifluoromethyloxy)biphenyl-2-yl group is more preferred.

As the substituent represented by R ³ in the general formula (1) of the europium complex B of the present invention, a cyclic secondary alkyl group having 3 to 10 carbon atoms or a fluorine atom is substituted in terms of good light resistance. a biphenylyl group optionally substituted with a fluoroalkyl group having 1 to 3 carbon atoms, a biphenylyl group optionally substituted with a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorine atom-substituted A phenyl group optionally substituted with a linear fluoroalkyl group, a phenyl group optionally substituted with a fluoroalkyloxy group having 1 to 3 carbon atoms are preferable, a cyclohexyl group, a phenyl group, 2-methylphenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 2',6'-dimethoxybiphenyl-2-yl group, 2',6'-bis(isopropoxy)biphenyl-2- yl group, 2′,4′,6′-triisopropylbiphenyl-2-yl group, 4′-fluorobiphenyl-2-yl group, 4′-(trifluoromethyl)biphenyl-2-yl group, or 4′ A -(trifluoromethyloxy)biphenyl-2-yl group is more preferred.

R ⁴ in the general formula (1) of the europium complexes A and B of the present invention represents a hydrogen atom, a deuterium atom or a fluorine atom, and is preferably a hydrogen atom in terms of easy availability.

The n in the general formula (1) of the europium complexes A and B of the present invention represents an integer of 1 to 3, and from the viewpoint that the europium complexes A and B of the present invention have good light resistance, n is preferably 2. .

The alkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in the general formula (1) of the europium complexes A and B of the present invention may be linear branched or cyclic. methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, 2 -methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group , cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group and the like.

The fluoroalkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in the general formula (1) of the europium complexes A and B of the present invention may be a linear, branched or cyclic fluoroalkyl group. often trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2, 3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2 , 3,3,3-hexafluoro-2-propyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorobutyl group, 2,2,3,3,4,4, 4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1- (trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoropentyl group, 2,2,3,3,4,4,5 , 5,5-nonafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5- trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-(1,1,2,2,2-pentafluoroethyl)propyl group, 1,2,2,3,3, 4,4,4-octafluoro-1-(trifluoromethyl)butyl group, 1,1,2,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butyl group, 1, 1,2,2,3,4,4,4-octafluoro-3-(trifluoromethyl)butyl group, 1,1,3,3,3-pentafluoro-2,2-bis(trifluoromethyl) propyl group, 2,2,3,3,3-pentafluoro-1,1-bis(trifluoromethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 1,2,2,3,3,4,4 ,5,5,5-decafluoro-1-(trifluoromethyl)pentyl group, 1,1,2,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl) pentyl group, 1,1,2,2,3,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pen Tyl group, 1,1,2,2,3,3,4,5,5,5-decafluoro-4-(trifluoromethyl)pentyl group, 2,2,3,3,4,4,4- heptafluoro-1,1-bis(trifluoromethyl)butyl group, 1,2,3,3,4,4,4-heptafluoro-1,2-bis(trifluoromethyl)butyl group, 1,2, 2,3,4,4,4-heptafluoro-1,3-bis(trifluoromethyl)butyl group, 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl fluoromethyl)butyl group, 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, 1,1,2,2,4,4,4- Examples include heptafluoro-3,3-bis(trifluoromethyl)butyl group, perfluorocyclohexyl group, and perfluorocyclopentylmethyl group.

As the substituents represented by W ¹ and W ² in the general formula (1) of the europium complexes A and B of the present invention, perfluoroalkyl groups having 1 to 6 carbon atoms are preferable in terms of good light resistance, and trifluoromethyl More preferred are radicals, perfluoroethyl radicals, and perfluoropropyl radicals.

Of the europium complexes A and B of the present invention, the europium complex B is preferred because it can be produced at low cost.

As the europium complex B of the present invention, both R ¹ and R ² are preferably cyclopentyl or cyclohexyl groups, and R ¹ , R ² and R ³ are all preferably cyclopentyl or cyclohexyl groups.

Specific examples of the europium complex B of the present invention include structures shown in the following (1-1) to (1-21), but the present invention is not limited thereto.

Among the compounds represented by (1-1) to (1-21), the europium complex B of the present invention has good light resistance (1-1) to (1-3), (1-4) to (1-8) is preferred, and (1-8) is particularly preferred because it can be easily synthesized from an inexpensive raw material, phosphorus trichloride, via phosphine oxide (4-8), and the production cost is low. .

Next, the production method of the europium complexes A and B of the present invention (hereinafter referred to as the production method of the present invention) will be described. As a method for producing the europium complexes A and B of the present invention, a phosphine oxide represented by the general formula (4) (hereinafter referred to as phosphine oxide (4)) and a β-diketone represented by the general formula (3) (hereinafter referred to as β-diketone (3)) and a europium salt are reacted.
(Step 1)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , n, W ¹ and W ² are R ¹ , R ² , R ³ , R ⁴ , n, W ¹ and W ² in general formula (1) has the same meaning as
In step 1, the cyclic alkyl group having 3 to 10 carbon atoms represented by R ¹ in general formula (4) is not particularly limited, but specific examples include cyclohexylmethyl group, cyclopropyl group, 2 , 3-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group , 3,5-dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, bicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octane-2- yl group, adamantan-1-yl group, adamantan-2-yl group and the like can be exemplified, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group or cyclodecanyl group etc. are preferred, and a cyclopentyl group or a cyclohexyl group is particularly preferred because of its good reaction yield.

In step 1, when R ² and R ³ in general formula (4) are cyclic alkyl groups having 3 to 10 carbon atoms, the cyclic alkyl groups having 3 to 10 carbon atoms are exemplified in the description of R ^1. The same as the cyclic alkyl group having 3 to 10 carbon atoms can be exemplified.

In step 1, the alkyl group having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in general formula (2a) may be linear or branched, Specific examples include, but are not limited to, methyl, ethyl, propyl and isopropyl groups.

In step 1, the alkyloxy group having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) is a linear or branched alkyloxy group. Any group may be used, and methoxy group, ethyloxy group, propyloxy group and 1-methylethyloxy group can be exemplified.

In step 1, the aryloxy groups having 6 to 10 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) are not particularly limited, but specific includes phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5- dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethyl phenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2, 3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethyl phenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group, 2,6-diethylphenyloxy group, 3,4 -diethylphenyloxy group, 3,5-diethylphenyloxy group, 2-propylphenyloxy group, 3-propylphenyloxy group, 4-propylphenyloxy group, 2-isopropylphenyloxy group, 3-isopropylphenyloxy group, 4-isopropylphenyloxy group, 2-cyclopropylphenyloxy group, 3-cyclopropylphenyloxy group, 4-cyclopropylphenyloxy group, 2-butylphenyloxy group, 3-butylphenyloxy group, 4-butylphenyloxy group 2-(1-methylpropyl)phenyloxy group, 3-(1-methylpropyl)phenyloxy group, 4-(1-methylpropyl)phenyloxy group, 2-(2-methylpropyl)phenyloxy group, 3-(2-methylpropyl)phenyloxy group, 4-(2-methylpropyl)phenyloxy group, 2-cyclobutylphenyloxy group, 3-cyclobutylphenyloxy group, 4-cyclobutylphenyloxy group and the like are exemplified. can do.

The fluoroalkyl groups having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) may be linear or branched fluoroalkyl groups, trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2,3 , 3,3-hexafluoro-2-propyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group and the like.

In step 1, the fluoroalkyloxy groups having 1 to 3 carbon atoms represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) are linear or branched fluoroalkyloxy any group, trifluoromethyloxy group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-difluoroethyloxy group group, perfluoropropyloxy group, 2,2,3,3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1 ,1-difluoropropyloxy group, 1,1,1,2,3,3,3-hexafluoro-2-propyloxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyloxy group, etc. can be exemplified.

In step 1, when one or more of X ¹ , X ² , X ³ , X ⁴ and X ⁵ in general formula (2a) is a phenyl group, the phenyl group is a fluorine atom or an alkyl group having 1 to 3 carbon atoms. group, alkyloxy group having 1 to 3 carbon atoms, aryloxy group having 6 to 10 carbon atoms, fluoroalkyl group having 1 to 3 carbon atoms, fluoroalkyloxy group having 1 to 3 carbon atoms, fluorophenyl group, hydroxyl group or cyano may be substituted with a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a fluoroalkyloxy group having 1 to 3 carbon atoms. group, a fluorophenyl group, a hydroxyl group, and a cyano group (hereinafter also referred to as a "substituted phenyl group"), the substituted phenyl group is 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 2,4,6-triisopropylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group , 4-(isopropyloxy)phenyl group, 2,6-di(isopropyloxy)phenyl group, 2-phenoxyphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 3,5-bis(trifluoromethyl)phenyl group, 2-(trifluoromethyloxy)phenyl group, 4-(trifluoromethyl) oxy)phenyl group, 2'-fluorobiphenyl-2-yl group, 4'-fluorobiphenyl-2-yl group, 4'-fluorobiphenyl-4-yl group, 3',5'-difluorobiphenyl-2-yl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group and 4-hydroxyphenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.

In step 1, the substituents represented by X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the general formula (2a) include a hydrogen atom, a fluorine atom and 1 to 3 carbon atoms in terms of good yield. Alkyl group, methoxy group, isopropoxy group, phenyl group optionally substituted with alkyl group having 1 to 3 carbon atoms, phenyl group optionally substituted with alkyloxy group having 1 to 3 carbon atoms, fluorine atom A phenyl group optionally substituted with a phenyl group optionally substituted with a linear fluoroalkyl group, a phenyl group optionally substituted with a linear fluoroalkyloxy group is preferred, a hydrogen atom, a methyl group , 2,4,6-triisopropylphenyl group, 2,6-dimethoxyphenyl group, 2,6-bis(isopropoxy)phenyl group, 4-fluorophenyl group, 4-(trifluoromethyl)phenyl group, 4- A (trifluoromethyloxy)phenyl group or a phenyl group is more preferred.

In step 1, as the substituents represented by R ² and R ³ in the general formula (4), a cyclic secondary alkyl group having 3 to 10 carbon atoms and a linear alkyl group are preferred because the reaction yield is good. A phenyl group which may be substituted, an alkyl group having 1 to 3 carbon atoms, or a biphenylyl group which may be substituted with an alkyloxy group having 1 to 3 carbon atoms are preferable, and a cyclohexyl group, a phenyl group and 2-methylphenyl group, 2,4,6-trimethylphenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 2′,6′-dimethoxybiphenyl-2-yl group, 2′,6′-bis(iso Propoxy)biphenyl-2-yl group and 2′,4′,6′-triisopropylbiphenyl-2-yl group are more preferred.

The phosphine oxide (4) used in step 1 can be obtained by the method described in Chemical Reviews, Vol. 60, pp. 243-260 (1960).

Specific examples of the phosphine oxide (4) used in step 1 include the structures shown in (4-1) to (4-21) below, but the present invention is not limited thereto. do not have.

Among the compounds represented by (4-1) to (4-21), the phosphine oxide (4) is represented by (4-1) to (4-3), (4-8) and (4-15). The compound obtained by the reaction is preferable in that the reaction yield is good.

In step 1, R ⁴ in general formula (3) represents a hydrogen atom, a deuterium atom, or a fluorine atom, and is preferably a hydrogen atom in terms of easy availability.

In step 1, the fluoroalkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in the general formula (3) may be a linear, branched or cyclic fluoroalkyl group, trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3 - pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2,3,3, 3-hexafluoro-2-propyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl) propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5- nonafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1-(1,1,2,2,2-pentafluoroethyl)propyl group, 1,2,2,3,3,4,4,4 -octafluoro-1-(trifluoromethyl)butyl group, 1,1,2,3,3,4,4,4-octafluoro-2-(trifluoromethyl)butyl group, 1,1,2,2 , 3,4,4,4-octafluoro-3-(trifluoromethyl)butyl group, 1,1,3,3,3-pentafluoro-2,2-bis(trifluoromethyl)propyl group, 2, 2,3,3,3-pentafluoro-1,1-bis(trifluoromethyl)propyl group, perfluorocyclopentyl group, perfluorohexyl group, 1,2,2,3,3,4,4,5,5, 5-decafluoro-1-(trifluoromethyl)pentyl group, 1,1,2,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)pentyl group, 1, 1,2,2,3,4,4,5,5,5-decafluoro-3-(trifluoromethyl)pentyl group, 1,1, 2,2,3,3,4,5,5,5-decafluoro-4-(trifluoromethyl)pentyl group, 2,2,3,3,4,4,4-heptafluoro-1,1- bis(trifluoromethyl)butyl group, 1,2,3,3,4,4,4-heptafluoro-1,2-bis(trifluoromethyl)butyl group, 1,2,2,3,4,4 ,4-heptafluoro-1,3-bis(trifluoromethyl)butyl group, 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl group, 1 , 2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, 1,1,2,2,4,4,4-heptafluoro-3,3- Bis(trifluoromethyl)butyl group, perfluorocyclohexyl group, perfluorocyclopentylmethyl group and the like can be exemplified.

In step 1, the substituents represented by W ¹ and W ² in the general formula (3) are preferably perfluoroalkyl groups having 1 to 6 carbon atoms from the viewpoint of good reaction yield, such as trifluoromethyl group and perfluoroethyl. and perfluoropropyl groups are more preferred.

Specific examples of the β-diketone (3) used in step 1 include hexafluoroacetylacetone (Hhfa), 1,1,1,5,5,6,6,6-octafluoro-2,4-hexanedione, 1,1,5,5-tetrafluoro-2,4-pentanedione, 1,1,1,2,2,3,3,7,7,8,8,9,9,9-tetradecafluoro- 4,6-nonanedione (Htdfn), 8H,8H-perfluoropentadecane-7,9-dione, trifluoroacetylacetone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro- 3,5-octanedione, acetylacetone, 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione , 1,3-diphenyl-1,3-propanedione, etc., but the present invention is not limited thereto.

The β-diketone (3) used in step 1 can be obtained, for example, by the method described in Journal of the American Chemical Society, Vol. 66, pp. 1220-1222, 1944. Moreover, you may use a commercial item. The β-diketone (3) has an active hydrogen atom and loses a hydrogen ion to become an anionic ligand. For example, hfa represents an anionic ligand depleted of a hydrogen ion from Hhfa, and tdfn represents an anionic ligand depleted of a hydrogen ion from Htdfn.

β-diketone (3) can undergo intramolecular hydrogen transfer to form enol (3a) or enol (3b), and β-diketone (3) of the present invention includes either enol. In this specification, β-diketone (3) is expressed as formula (3).

The europium salt used in step 1 is not particularly limited, but examples include halides such as europium (III) fluoride, europium (III) chloride, europium (III) bromide, and europium (III) iodide organic acid salts such as salts and hydrates thereof, europium oxalate (III), europium acetate (III), europium trifluoroacetate (III), europium methanetrifluorosulfonate (III) and hydrates thereof; Metal alkoxides such as tris[N,N-bis(trimethylsilyl)amide]europium(III), europium(III) trimethoxide, europium(III) triethoxide, europium(III) tri(2-propoxide), europium(III) phosphate ), europium (III) sulfate, europium (III) nitrate and other inorganic acid salts and hydrates thereof. Among them, europium chloride (III), europium nitrate (III) or europium oxalate (III), europium acetate (III), europium trifluoroacetate (III), europium methanetrifluorosulfonate (III ) are preferred, and europium (III) acetate, europium (III) chloride, and europium (III) nitrate are more preferred.

In step 1, n in general formula (1) represents an integer of 1 to 3, and n is preferably 2 from the standpoint of good reaction yield.

In Step 1, the reaction yield of the europium complexes A and B of the present invention is good, so it is preferable to carry out the step in a solvent. There are no particular restrictions on the types of solvents that can be used as long as they do not inhibit the reaction. Examples of usable solvents include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; alcohols such as methanol, ethanol, propanol and isopropyl alcohol; esters such as methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate; Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, tetrahydrofuran, cyclopentyl methyl ether, tert-butyl methyl Ketones such as ketones, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone and acetone, hydrocarbons such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene and xylene, and water. can be mentioned. These solvents may be used singly or as a mixture of two or more at any ratio. Dichloromethane, chloroform, methanol, or ethanol is preferable as the solvent because the reaction yield of the europium complexes A and B of the present invention is good.

Next, in step 1, the molar ratio of the europium salt and the phosphine oxide (4) will be explained. It is preferable to use 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol of phosphine oxide (4) per 1 mol of europium salt.

In step 1, the molar ratio of europium salt and β-diketone (3) is explained. It is preferable to use 1.0 to 10 mol, more preferably 2.0 to 8.0 mol of β-diketone (3) per 1 mol of europium salt.

In step 1, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing metal complexes. As a specific example, the europium complexes A and B of the present invention can be obtained by selecting a reaction temperature appropriately selected from the temperature range of −80° C. to 120° C. and a reaction time appropriately selected from the range of 1 minute to 120 hours. It can be manufactured efficiently.

The europium complexes A and B of the present invention produced in step 1 can be purified by appropriately selecting and using a general purification method for purifying metal complexes by those skilled in the art. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

Further, as the production method of the present invention, a step 2 characterized by reacting the diketonato complex (5) and the phosphine oxide (4) can also be mentioned.
(Step 2)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , n, W ¹ and W ² are R ¹ , R ² , R ³ , R ⁴ , n, W ¹ and W ² of general formula (1) have the same meaning, Q represents a coordination molecule, and m represents a number from 0 to 3.)
In step 2, the coordinating molecule represented by Q is not limited as long as it does not inhibit the reaction. Specific examples include water, heavy water, tetrahydrofuran, pyridine, imidazole, acetone, methanol, ethanol, propanol, isopropyl alcohol, Nitriles such as acetonitrile and propionitrile; amines such as ammonia, diethylamine and triethylamine; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; Water is preferred.

m of the diketonato complex (5) is preferably 2 from the viewpoint of ease of synthesis.

The diketonato complex (5) used in step 2 can be obtained by the method described in Reference Example 1 of this specification or the method described in Journal of the American Chemical Society, Vol. 87, pp. 5254-5256, 1965. can be done.

Specific examples of the diketonato complex (5) used in step 2 include tris(hexafluoroacetylacetonato)europium (III), tris(1,1,1,5,5,6,6,6-octafluoro -2,4-dioxohexan-3-ido) europium (III), tris(1,1,5,5-tetrafluoro-2,4-dioxopentan-3-ido) europium (III), tris ( 1,1,1,2,2,3,3,7,7,8,8,9,9,9-tetradecafluoro-4,6-dioxononan-5-ido)europium (III), tris (1 , 1, 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 10, 10, 11, 11, 12, 12, 13, 13, 14, 14, 15, 15, 15 -hexacosafluoro-7,9-dioxopentadecane-8-ido)europium(III), tris(trifluoroacetylacetonato)europium(III), tris[4,4,4-trifluoro-1-(2 -thienyl)-1,3-dioxobutan-2-ido]europium (III), tris(4,4,4-trifluoro-1-phenyl-1,3-dioxobutan-2-ido)europium (III), tris Examples include (1,3-diphenyl-1,3-dioxopropan-2-ido)europium (III) and hydrates thereof, but the present invention is not limited thereto.

The phosphine oxide (4) used in step 2 can be obtained by the method described in Reference Example 3 of this specification, Chemical Reviews, Vol. 60, pp. 243-260, 1960 and Organic Letters, Vol. 2011, etc. can be obtained by the method described.

As the phosphine oxide (4) used in step 2, the same phosphine oxides as those exemplified in step 1 can be exemplified, but the present invention is not limited thereto. In step 2, R ¹ , R ² and R ³ are preferably cyclohexyl groups in terms of good reaction yield.

In Step 2, it is preferable to carry out the reaction in a solvent because the reaction yield of the europium complexes A and B of the present invention is good. There are no particular restrictions on the types of solvents that can be used as long as they do not inhibit the reaction. Examples of usable solvents include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; alcohols such as methanol, ethanol, propanol and isopropyl alcohol; esters such as ethyl acetate, butyl acetate and isoamyl acetate; Glycol ethers such as ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, tetrahydrofuran, tert-butyl methyl ketone, isobutyl methyl ketone, ethyl Examples include ketones such as butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone and acetone, hydrocarbons such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene and xylene, and water. These solvents can be used alone or in combination of two or more at any ratio. Dichloromethane, chloroform, methanol, or ethanol is preferable as the solvent because the reaction yield of the europium complexes A and B of the present invention is good.

Next, the molar ratio of the diketonato complex (5) and the phosphine oxide (4) when carrying out step 2 will be explained. It is preferable to use 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol of phosphine oxide (4) per 1 mol of diketonato complex (5).

In step 2, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing metal complexes. As a specific example, the europium complexes A and B of the present invention are reacted at a reaction temperature appropriately selected from the temperature range of −80° C. to 120° C. by selecting the reaction time appropriately selected from the range of 1 minute to 120 hours. It can be produced with good yield.

The europium complexes A and B of the present invention produced in step 2 can be purified by appropriately selecting and using a general purification method for purifying metal complexes by those skilled in the art. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

The europium complexes A and B of the present invention are useful as optical materials containing the europium complexes A and B of the present invention, since they exhibit the feature of being resistant to deterioration even when exposed to sunlight, ultraviolet light, or the like for a long period of time. As optical materials, wavelength conversion materials used for films for solar cells, films for agriculture, LED phosphors, organic EL materials, security inks and the like are particularly useful.

In addition, the europium complexes A and B of the present invention can be used as an optical material containing one or more selected from resin materials, inorganic glasses, and organic low-molecular-weight materials. is particularly preferred. Examples of the resin material include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, fluorine-containing polymethyl methacrylate, fluorine-containing Polymethacrylates such as polyethyl methacrylate, fluorine-containing polypropyl methacrylate, fluorine-containing polyisopropyl methacrylate, fluorine-containing polybutyl methacrylate, fluorine-containing polysec-butyl methacrylate, fluorine-containing polyisobutyl methacrylate, fluorine-containing polytert-butyl methacrylate, polymethyl Acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, fluorine-containing polymethyl acrylate, fluorine-containing polyethyl acrylate, fluorine-containing polypropyl Polyacrylates such as acrylates, fluorine-containing polyisopropyl acrylate, fluorine-containing polybutyl acrylate, fluorine-containing polysec-butyl acrylate, fluorine-containing polyisobutyl acrylate, fluorine-containing polytert-butyl acrylate, polystyrene, polyethylene, polypropylene, polybutene, fluorine-containing Polyolefins such as polyethylene, fluorine-containing polypropylene, fluorine-containing polybutene, polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, and copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, Polyimide resin, polyurethane, Nafion, petroleum resin, rosin, silicon resin, etc. are exemplified, among which polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate. , poly tert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, poly sec-butyl acrylate, polyisobutyl acrylate, poly tert-butyl acrylate , polyethylene, polystyrene, polyvinyl acetate and copolymers thereof are preferred, and polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, Polyethylene, polystyrene, polyvinyl acetate and copolymers thereof are particularly preferred. These may be used alone or in combination of two or more.

Among these resin materials, particularly preferably used polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polystyrene, polyvinyl acetate and their co-polymers The polymer is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, styrene, or vinyl acetate. , can be obtained by suspension polymerization in water for 3 to 8 hours.

The polymerization initiator to be used may be one that is commonly used by those skilled in the art when polymerizing these resin materials. Organic peroxides can be mentioned.

In the suspension polymerization, it is preferable to add a dispersion stabilizer in order to prevent aggregation of the polymer particles obtained. Examples include water-sparingly water-soluble inorganic fine particles such as aluminum oxide and magnesium carbonate, polyacrylates, polymethacrylates, polyacrylamides, polyvinyl alcohols, and cellulose derivatives.

In the suspension polymerization, it is preferable to add a polymerization modifier to prevent the suppression of the gelled product. Examples include nitroxyl compounds such as 2,6,6-tetramethylpiperidine-1-oxyl, nitrites such as sodium nitrite, and nitrogen oxides such as di-tert-butyl nitroxide.

The ratio of the europium complexes A and B in the optical material containing the europium complexes A and B of the present invention and a resin material is preferably 0.001 to 99% by weight, more preferably 0.01 to 10% by weight.

As the inorganic glass, those commonly used by those skilled in the art may be used, and examples thereof include soda glass, crystal glass, borosilicate glass, and the like.

As the organic low-molecular-weight material, those commonly used by those skilled in the art may be used, for example, ionic liquids such as amyltriethylammonium bis(trifluoromethanesulfonyl)imide, tetraamyl ammonium chloride, pentadecane, hexadecane, octadecane, nonadecane, icosane, paraffin, etc. and hydrocarbons.

The method of obtaining an optical material containing the europium complexes A and B of the present invention includes a method of using the europium complexes A and B alone to form an optical material, and a method of using the europium complexes A and B as a resin material, an inorganic glass, or an organic low-molecular-weight material. A method of making an optical material by incorporating it in an optical material containing one or more selected from materials, and an optical material by mixing the corresponding monomers and the europium complexes A and B when polymerizing the above resin material and polymerizing the monomers. and a method of dissolving and dispersing the europium complexes A and B in a solvent to form an optical material.

When the europium complexes A and B of the present invention are dissolved and dispersed in a solvent to form an optical material, the solvents that can be used include, for example, halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, methanol, ethanol, propanol, alcohols such as isopropyl alcohol; esters such as ethyl acetate, butyl acetate and isoamyl acetate; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; Ethers such as glyme, diglyme, triglyme, and tetrahydrofuran, ketones such as tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, and acetone, hexane, cyclohexane, ethylcyclohexane, heptane, Hydrocarbons such as octane, benzene, toluene, xylene, and water may be mentioned. These solvents can be used alone or in combination of two or more at any ratio.

The europium complexes A and B of the present invention become compounds having excellent light resistance by introducing a specific substituent on the phosphorus atom, and are resistant to deterioration even when exposed to sunlight, ultraviolet light, etc. for a long period of time. Since it has light resistance, it is a promising wavelength conversion material that can be used for a long time.

1 is an emission spectrum of the europium complex of the present invention obtained in Example 1. FIG. 4 is an emission spectrum of the europium complex of the present invention obtained in Example 2. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 3. FIG. 4 is an emission spectrum of the europium complex of the present invention obtained in Example 4. FIG. 4 is an emission spectrum of the europium complex of the present invention obtained in Example 5. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 6. FIG. 4 is an emission spectrum of the europium complex of the present invention obtained in Example 7. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 8. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 9. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 10. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 11. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 12. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 13. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 14. FIG. 3 is an emission spectrum of the europium complex of the present invention obtained in Example 17. FIG. 1 is an emission spectrum of an optical material containing a europium complex of the present invention obtained in Production Example 1. FIG. 4 is an emission spectrum of the optical material containing the europium complex of the present invention obtained in Production Example 2. FIG. 3 is an emission spectrum of the optical material containing the europium complex of the present invention obtained in Production Example 3. FIG. 1 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 1. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 2. FIG. 4 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 3. FIG. 4 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 4. FIG. 4 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 5. FIG. 4 shows the evaluation results of the light resistance test of the europium complex of the present invention obtained in Example 6. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 7. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 8. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 9. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 10. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 11. FIG. 12 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 12. FIG. 2 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 13. FIG. 4 shows the results of a light resistance test evaluation of the europium complex of the present invention obtained in Example 14. FIG.

EXAMPLES The present invention will be described in more detail below with reference to examples, comparative examples, and evaluation examples, but the present invention should not be construed as being limited thereto. Note that Cy represents a cyclohexyl group in the chemical formula.

The following analytical methods were used to identify the europium complexes of the present invention.

BRUKER ULTRASHIELD PLUS AVANCE III (400 MHz, 376 MHz and 162 MHz) and ASCEND AVANCE III HD (400 MHz, 376 MHz and 162 MHz) were used for ¹ H-NMR, ¹⁹ F-NMR and ³¹ P-NMR measurements. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. ¹⁹ F-NMR was measured using deuterated chloroform (CDCl ₃ ) and deuterated acetone (Acetone-d ₆ ) as measurement solvents. ³¹ P-NMR was measured using deuterated chloroform (CDCl ₃ ).

Mass spectrometric measurements were performed using waters 2695-micromass ZQ4000 manufactured by Waters.

A spectrophotometer (manufactured by JASCO Corporation, FP-6500) was used to measure the emission spectrum.

The emission quantum yield was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics, C9920-03).

Commercially available reagents were used.

Reference example 1

2-Biphenylyl(dicyclohexyl)phosphine (1.50 g, 4.28 mmol) was dissolved in dichloromethane (15 mL), 30% aqueous hydrogen peroxide (1.0 mL) was added, and the mixture was stirred at room temperature for 1 hour. Water (15 mL) was added to the reaction mixture, the organic layer was separated, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give 2-biphenylyl(dicyclohexyl)phosphine oxide as a white solid (1.58 g, yield >99%). . ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 8.11 (m, 1H), 7.53-7.46 (m, 2H), 7.45-7.33 (m, 3H) , 7.25 to 7.19 (m, 3H), 1.88 to 1.78 (m, 2H), 1.78 to 1.46 (m, 8H), 1.45 to 0.96 (m, 12H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 48.3 (s).

Reference example 2

Dicyclohexylphenylphosphine (580 mg, 2.11 mmol) was dissolved in dichloromethane (8.0 mL), 30% hydrogen peroxide solution (0.80 mL) was added, and the mixture was stirred at room temperature for 3 hours. Water (8 mL) was added to the reaction mixture, the organic layer was separated, chloroform (8 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give dicyclohexylphenylphosphine oxide (440 mg, yield 72%) as a white solid. ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.66 (brt, J=8.0 Hz, 2H), 7.55-7.44 (m, 3H), 2.12-1. 97 (m, 4H), 1.88-1.55 (m, 8H), 1.38-1.08 (m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 45.3 (s).

Reference example 3

Dicyclohexyl(2-methylphenyl)phosphine (577 mg, 2.0 mmol) was dissolved in dichloromethane (4.0 mL), cooled to 0° C., 30% hydrogen peroxide solution (1.0 mL) was added, and Stirred for an hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain a white solid of dicyclohexyl(2-methylphenyl)phosphine oxide (486 mg, 80% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.48-7.42 (m, 1H), 7.37 (t, J=7.6 Hz, 1H), 7.25-7. 21 (m, 2H), 2.66 (s, 3H), 2.13-2.00 (m, 4H), 1.89-1.54 (m, 8H), 1.48-1.09 ( m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 49.3 (s).

Reference example 4

Dicyclohexyl(2,4,6-trimethylphenyl)phosphine (475 mg, 1.5 mmol) was dissolved in dichloromethane (3.0 mL), cooled to 0°C, and 30% hydrogen peroxide solution (1.0 mL) was added. at room temperature for 1 hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain a white solid of dicyclohexyl(2,4,6-trimethylphenyl)phosphine oxide (yield: 605 mg, yield: >99%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 6.85 (s, 2H), 2.55 (s, 6H), 2.27 (s, 3H), 2.08-1.99 (m, 4H), 1.89-1.62 (m, 8H), 1.49-1.11 (m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 52.8 (s).

Reference example 5

2-(Dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (412 mg, 1.0 mmol) was dissolved in dichloromethane (5.0 mL), 30% hydrogen peroxide solution (2.4 mL) was added, and the mixture was stirred at room temperature. Stirred for 17 hours. Water (15 mL) was added to the reaction mixture, the organic layer was separated, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain a white solid of dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine oxide (yield: 386 mg, 90% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.54-7.46 (m, 1H), 7.34-7.28 (t, J=8.2 Hz, 1H),7. 16 ~ 7.12 (m, 1H), 6.60 (d, J = 8.5Hz, 6H), 3.68 (s, 6H), 1.79 ~ 1.39 (m, 12H), 1. 38-1.24 (m, 2H), 1.20-1.01 (m, 6H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 46.6 (s).
Reference example 6

Dicyclohexyl(2′,6′-diisopropoxybiphenyl-2-yl)phosphine (500 mg, 1.1 mmol) was dissolved in dichloromethane (4.0 mL), cooled to 0° C., and then dissolved in 30% aqueous hydrogen peroxide ( 1.0 mL) was added and stirred at room temperature for 1 hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give a colorless oil of dicyclohexyl(2',6'-diisopropoxybiphenyl-2-yl)phosphine oxide. (572 mg, >99% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.92-7.86 (m, 1H), 7.44-7.34 (m, 2H), 7.21 (t, J = 8.4Hz, 1H), 7.05-7.00 (m, 1H), 6.59 (d, J = 8.4Hz, 2H), 4.38 (sept, J = 6.0Hz, 2H), 1.80-1.00 (m, 34H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 46.
7(s).

Reference example 7

2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (716 mg, 1.5 mmol) was dissolved in dichloromethane (5.0 mL), 30% hydrogen peroxide solution (3.6 mL) was added, Stir at room temperature for 17 hours. Water (15 mL) was added to the reaction mixture, the organic layer was separated, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give dicyclohexyl(2',4',6'-triisopropylbiphenyl-2-yl)phosphine oxide as a white solid. (yield 588 mg, yield 80%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.72-7.63 (m, 1H), 7.48-7.36 (m, 2H), 7.20-7.14 ( m, 1H), 7.01-6.95 (m, 2H), 2.97-2.80 (m, 1H), 2.45-2.30 (m, 2H), 1.93-1. 79 (m, 4H), 1.78-1.67 (m, 8H), 1.44-1.33 (m, 4H), 1.32-1.22 (m, 12H), 1.21- 1.08 (m, 6H), 0.96 (d, J=6.7Hz, 6H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 44.4 (s).

Reference example 8

Tricyclohexylphosphine (1.66 g, 5.9 mmol) was dissolved in dichloromethane (10 mL), 30% aqueous hydrogen peroxide (3.0 mL) was added, and the mixture was stirred at room temperature for 1 hour.Water (15 mL) was added to the reaction mixture. After separating the organic layer, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated.This procedure was repeated twice.The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure.The obtained crude product was By purifying the product by silica gel column chromatography (eluent: chloroform/methanol), a white solid of tricyclohexylphosphine oxide was obtained ( ^yield : 1.24 g, yield: 71%). CDCl ₃ ), δ (ppm): 1.94-1.73 (m, 18H), 1.48-1.25 (m, 15H) ^.31 P-NMR (162 MHz, CDCl ₃ ), δ (ppm) : 50.0 (s).

Reference example 9

Tricyclopentylphosphine (1.00 g, 4.20 mmol) was charged and dissolved in dichloromethane (26 mL). After cooling the solution to 0° C., 30% hydrogen peroxide solution (1.3 mL) was added, and the mixture was stirred at 0° C. for 15 minutes and at room temperature for 2 hours. Water (13 mL) was added to the reaction mixture, the organic layer was separated, chloroform (26 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain a white solid of tricyclopentylphosphine oxide (653 mg, 61% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 2.16-2.02 (m, 3H), 1.95-1.51 (m, 24H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 54.0 (s, 1P).

Reference example 10

Under an argon atmosphere, chlorodicyclohexylphosphine (2.2 mL, 10 mmol) was dissolved in tetrahydrofuran (50 mL), water (5.0 mL) was added, and the mixture was stirred at room temperature for 2 hours. After removing the solvent by concentration, chloroform (20 mL) was added to the reaction mixture and the chloroform layer was separated. This operation was repeated twice. The organic layer was dried over sodium sulfate and then concentrated under reduced pressure to obtain a white solid of dicyclohexylphosphine oxide (yield: 2.04 g, yield: 95%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 6.31 (d, J _PH =433.5 Hz, 1H), 2.01-1.65 (m, 12H), 1.57-1 .19(m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 49.4 (s).

Under an argon atmosphere, dicyclohexylphosphine oxide (1.5 g, 7.0 mmol), 1-bromo-2-iodobenzene (0.88 mL, 7.0 mmol), copper (I) iodide (267 mg, 1.4 mmol) and 2 ,2′-bipyridyl (219 mg, 1.4 mmol) was added with toluene (25 mL) and stirred at room temperature for 5 minutes. Cesium carbonate (4.56 g, 14 mmol) was added to the reaction mixture and stirred at 100° C. for 21 hours. After removing insoluble matter by filtration, the reaction mixture was added with chloroform (30 mL) and washed with 1M hydrochloric acid (30 mL) three times. The separated organic layer was dried over sodium sulfate and then concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give (2-bromophenyl)dicyclohexylphosphine oxide as a white solid (6.07 g, 70% yield). ). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 8.13 (ddd, J = 10.6, 7.6, 1.8 Hz, 1H), 7.59 (dd, J = 7.6 , 3.4 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 1 H), 7.34 (t, J = 7.6 Hz, 1 H), 2.51 to 2.40 (m, 2 H) , 2.16 to 2.05 (m, 2H), 1.92 to 1.81 (m, 2H), 1.78 to 1.59 (m, 6H), 1.44 to 1.14 (m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 48.7 (s).

Reference example 11

Under an argon atmosphere, (2-bromophenyl)dicyclohexylphosphine oxide (369 mg, 1.0 mmol) obtained in Reference Example 10, 4-fluorophenylboronic acid (280 mg, 2.0 mmol), dicyclohexyl (2',6'-di Toluene (isopropoxybiphenyl-2-yl)phosphine (37 mg, 0.08 mmol), tripotassium phosphate (637 mg, 3.0 mmol) and tris(dibenzylideneacetone) dipalladium (0) (18 mg, 0.020 mmol) 4.0 mL) was added and stirred at 100° C. for 19 hours. Water (10 mL) was added to the reaction mixture. Chloroform (10 mL) was added to the aqueous layer and the chloroform layer was separated. This operation was repeated three times. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give (4'-fluoro-[1,1'-biphenyl]-2-yl)dicyclohexylphosphine oxide as a white solid. (Yield 339 mg, Yield 88%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.99 (m, 1H), 7.52-7.46 (m, 2H), 7.24-7.17 (m, 3H) , 7.13-7.07 (m, 2H), 1.90-1.01 (m, 22H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −114.3 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 47.8 (s).

Reference example 12

(2-Bromophenyl)dicyclohexylphosphine oxide (369 mg, 1.0 mmol) obtained in Reference Example 10, 4-(trifluoromethyl)phenylboronic acid (379 mg, 2.0 mmol), triphenylphosphine (31 mg) were dissolved under an argon atmosphere. , 0.12 mmol), tripotassium phosphate (637 mg, 3.0 mmol) and bis(dibenzylideneacetone)palladium(0) (17 mg, 0.030 mmol) were added with 1,4-dioxane (3.4 mL). C. for 14 hours. Water (20 mL) was added to the reaction mixture. Chloroform (20 mL) was added to the aqueous layer and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. By purifying the obtained crude product by silica gel column chromatography (eluent: hexane/ethyl acetate), (4'-trifluoromethyl-[1,1'-biphenyl]-2-yl)dicyclohexylphosphine oxide of white solid was obtained (yield 204 mg, yield 47%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.84 (m, 1H), 7.65 (d, J = 8.0 Hz, 2H), 7.53-7.50 (m, 2H), 7.38 (d, J=8.0 Hz, 2H), 7.21 (m, 1H), 1.87-1.05 (m, 22H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −62.4 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 47.3 (s).

Reference example 13

Under an argon atmosphere, 3-bromobiphenyl (513 mg, 2.2 mmol) was dissolved in diethyl ether (5.0 mL) and cooled to -20°C. A 2.67M hexane solution of n-butyllithium (0.85 mL, 2.3 mmol) was added dropwise to this solution, and after stirring for 2 hours, chlorodicyclohexylphosphine (0.44 mL, 2.0 mmol) was added, and the temperature was raised to room temperature. It was warmed and stirred for 6 hours. The reaction mixture was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain a white solid of 3-biphenylyl(dicyclohexyl)phosphine (yield: 645 mg, Yield 92%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.68 (d, J=7.6 Hz, 1H), 7.63-7.54 (m, 3H), 7.49-7. 33 (m, 5H), 2.00-0.98 (m, 22H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 3.68 (s).

Dissolve 3-biphenylyl(dicyclohexyl)phosphine (631 mg, 1.8 mmol) in dichloromethane (4.0 mL), cool to 0° C., add 30% aqueous hydrogen peroxide (1.0 mL), and stir at room temperature for 1 hour. Stirred. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give 3-biphenylyl(dicyclohexyl)phosphine oxide as a white solid (969 mg, >99% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.89 (d, J=10 Hz, 1 H), 7.74 (d, J=7.5 Hz, 1 H), 7.65-7. 58 (m, 3H), 7.54 (td, J = 7.5, 2.8Hz, 1H), 7.47 (t, J = 7.5Hz, 2H), 7.39 (t, J = 7 .5Hz, 1H), 2.13-2.01 (m, 4H), 1.88-1.61 (m, 8H), 1.40-1.09 (m, 10H). ³¹ P-NMR (162 MHz, CDCl3) δ (ppm): 45.0 (s).

Reference example 14

Under an argon atmosphere, 4-bromobiphenyl (513 mg, 2.2 mmol) was dissolved in diethyl ether (5.0 mL) and cooled to -20°C. A 2.67M hexane solution of n-butyllithium (0.85 mL, 2.3 mmol) was added dropwise to this solution, and after stirring for 2 hours, chlorodicyclohexylphosphine (0.44 mL, 2.0 mmol) was added, and the temperature was raised to room temperature. It was warmed and stirred for 6 hours. The reaction mixture was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain a white solid of 4-biphenylyl(dicyclohexyl)phosphine (yield: 592 mg, Yield 85%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.72 (m, 1H), 7.65-7.59 (m, 2H), 7.59-7.49 (m, 3H) , 7.48-7.32 (m, 3H), 2.12-1.54 (m, 12H), 1.41-0.96 (m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 2.19 (s).

4-Biphenylyl(dicyclohexyl)phosphine (592 mg, 1.7 mmol) was dissolved in dichloromethane (4.0 mL), cooled to 0° C., 30% hydrogen peroxide solution (1.0 mL) was added, and the mixture was stirred at room temperature for 1 hour. Stirred. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to give 4-biphenylyl(dicyclohexyl)phosphine oxide as a white solid (yield: 612 mg, >99%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.76-7.67 (m, 4H), 7.65-7.61 (m, 2H), 7.50-7.44 ( m, 2H), 7.39 (m, 1H), 2.14-1.99 (m, 4H), 1.90-1.61 (m, 8H), 1.41-1.09 (m, 10H). ³¹ P-NMR (162 MHz, CDCl3) δ (ppm): 45.0 (s).

Reference example 15

Under an argon atmosphere, 2-bromodiphenyl ether (498 mg, 2.0 mmol) was dissolved in tetrahydrofuran (16.0 mL) and cooled to -80°C. A 2.67M hexane solution of n-butyllithium (0.77 mL, 2.1 mmol) was added dropwise to this solution and stirred for 3 hours. Stir warmed for 18 hours. Water (20 mL) was added to the reaction mixture. Dichloromethane (20 mL) was added to the aqueous layer and the dichloromethane layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain a white solid of dicyclohexyl(2-phenoxyphenyl)phosphine (678 mg, 93% yield). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.50 (m, 1H), 7.36-7.24 (m, 3H), 7.11-7.05 (m, 2H) , 6.99 to 6.93 (m, 2H), 6.82 (m, 1H), 2.11 to 2.00 (m, 2H), 1.92 to 1.57 (m, 10H), 1 .33-1.01 (m, 10H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −6.60 (s).

Dicyclohexyl(2-phenoxyphenyl)phosphine (678 mg, 1.9 mmol) was dissolved in dichloromethane (4.0 mL), cooled to 0° C., 30% aqueous hydrogen peroxide (1.0 mL) was added, and Stirred for an hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain a white solid of dicyclohexyl(2-phenoxyphenyl)phosphine oxide (yield: 533 mg, yield: 75%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 8.04 (m, 1H), 7.44-7.35 (m, 3H), 7.24-7.17 (m, 2H) , 7.05 to 7.00 (m, 2H), 6.74 (m, 1H), 2.26 to 2.02 (m, 4H), 1.87 to 1.57 (m, 8H), 1 .55-1.37 (m, 4H), 1.31-1.05 (m, 6H). ³¹ P-NMR (162 MHz, CDCl3) δ (ppm): 47.9 (s).

Reference example 16

Pure water (100 mL) was added to europium acetate n-hydrate (8.0 g, 21 mmol as 2.5 hydrate) under an argon atmosphere, and the mixture was stirred at room temperature for 10 minutes. After Hhfa (16.7 g, 80.2 mmol) was added dropwise to the reaction mixture, the mixture was stirred at 50°C for 3 hours. The resulting white suspension was filtered, and the resulting white solid was washed with water (200 mL) and toluene (200 mL) to give diaquatris(hexafluoroacetylacetonato)europium (III) as a white solid. (Yield: 11.6 g, yield: 68% assuming that 21 mmol of europium acetate 2.5 hydrate was used). ¹⁹ F-NMR (376 MHz, Acetone-d ₆ ), δ (ppm): −81.2 (brs). ESIMS (m/z): 566.8 [M-hfa] ⁺ .

Reference example 17

Di(1-adamantyl)-2-biphenylphosphine (256 mg, 0.56 mmol) was dissolved in dichloromethane (5 mL), 30% hydrogen peroxide solution (1.0 mL) was added, and the mixture was stirred at room temperature for 1 hour. Water (15 mL) was added to the reaction mixture, the organic layer was separated, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain a white solid of di(1-adamantyl)-2-biphenylphosphine oxide (yield: 172 mg, yield: 66%). ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.60 (brd, J = 8.2, 7.7 Hz, 1H), 7.46 (brd, J = 7.7, 7.7 Hz, 1H), 7.39 (brdd, J=7.7, 7.5Hz, 1H), 7.32-7.17 (m, 6H), 2.12-1.88 (m, 18H), 1. 80-1.60 (m, 12H). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): 44.3.

Example 1

Under an argon atmosphere, europium acetate n-hydrate (170 mg, 0.46 mmol as 2.5 hydrate) and (2-biphenylyl)dicyclohexylphosphine oxide (338 mg, 0.92 mmol) obtained in Reference Example 1 were mixed with dichloromethane (8 .0 mL) was added and stirred at room temperature for 30 minutes. A 0.30 M dichloromethane solution of Hhfa (4.7 mL, 1.4 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. Hexane is added to the reaction solution, left at room temperature, and the precipitated solid is collected by filtration to give a reddish white color of bis[(2-biphenylyl)dicyclohexylphosphine oxide)]tris(hexafluoroacetylacetonato)europium (III). A solid was obtained (yield 483 mg, 35% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.4 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −81.1 (brs). ESIMS (m/z): 1297.6 [M-hfa] ⁺ .

Example 2

Under an argon atmosphere, europium acetate n-hydrate (132 mg, 0.40 mmol as 2.5 hydrate) and dicyclohexylphenylphosphine oxide (232 mg, 0.80 mmol) obtained in Reference Example 2 were mixed with dichloromethane (5.0 mL). and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.67 mL, 1.2 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure and recrystallized with methanol to obtain a reddish white solid of bis(dicyclohexylphenylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III). (381 mg yield, 70% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.3 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −80.6 (brs). ESIMS (m/z): 1147.7 [M-hfa] ⁺ .

Example 3

Under an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and dicyclohexyl(2-methylphenyl)phosphine oxide (183 mg, 0.60 mmol) obtained in Reference Example 3 were mixed with dichloromethane ( 3.0 mL) was added and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.5 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure and recrystallized with dichloromethane/acetonitrile to obtain a reddish white solid of bis[dicyclohexyl-(2-methylphenyl)phosphine oxide]tris(hexafluoroacetylacetonato)europium (III) ( Yield 321 mg, yield 77%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.4 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −76.3 (brs). ESIMS (m/z): 1175.3 [M-hfa] ⁺ .

Example 4

Under an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and dicyclohexyl(2,4,6-trimethylphenyl)phosphine oxide obtained in Reference Example 4 (199 mg, 0.60 mmol) ) was added with dichloromethane (3.0 mL) and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.5 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was concentrated under reduced pressure and recrystallized from dichloromethane/acetonitrile to give bis[dicyclohexyl-(2,4,6-trimethylphenyl)phosphine oxide]tris(hexafluoroacetylacetonato)europium (III) as a reddish white solid. (Yield 162 mg, Yield 38%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −79.1 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −71.6 (brs). ESIMS (m/z): 1231.3 [M-hfa] ⁺ .

Example 5

Under an argon atmosphere, europium acetate n-hydrate (100 mg as 2.5 hydrate, 0.30 mmol) and dicyclohexyl (2′,6′-dimethoxybiphenyl-2-yl)phosphine oxide (257 mg) obtained in Reference Example 5 , 0.60 mmol) was added with dichloromethane (5 mL) and stirred at room temperature for 30 minutes. A 1.8 M dichloromethane solution of Hhfa (0.5 mL, 0.9 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. After removing insoluble matter by filtration, the reaction mixture was concentrated under reduced pressure and washed with hexane to give bis[dicyclohexyl-(2′,6′-dimethoxybiphenyl-2-yl)phosphine oxide]tris(hexafluoroacetylacetoate). Nath) Europium (III) was obtained as a reddish-white solid (332 mg, 67% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.5 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −84.0 (brs). ESIMS (m/z): 1419.7 [M-hfa] ⁺ .

Example 6

Under an argon atmosphere, europium acetate n-hydrate (58 mg, 0.16 mmol as 2.5 hydrate) and dicyclohexyl(2′,6′-diisopropoxybiphenyl-2-yl)phosphine oxide obtained in Reference Example 6 Dichloromethane (2.0 mL) was added to (153 mg, 0.32 mmol) and stirred at room temperature for 1 hour. A 1.0 M dichloromethane solution of Hhfa (0.48 mL, 0.48 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was concentrated under reduced pressure and recrystallized from dichloromethane/methanol to give bis[dicyclohexyl(2′,6′-diisopropoxybiphenyl-2-yl)phosphine oxide]tris(hexafluoroacetylacetonato)europium (III). ) was obtained as a reddish-white solid (yield: 172 mg, yield: 64%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.1 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −85.4 (brs). ESIMS (m/z): 1531.1 [M-hfa] ⁺ .

Example 7

Under an argon atmosphere, europium acetate n-hydrate (99 mg as 2.5 hydrate, 0.30 mmol) and dicyclohexyl (2′,4′,6′-triisopropylbiphenyl-2-yl) obtained in Reference Example 7 Dichloromethane (5.0 mL) was added to phosphine oxide (296 mg, 0.60 mmol) and stirred at room temperature for 30 minutes. A solution of Hhfa in dichloromethane (1.8 M, 0.5 mL, 0.9 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. After removing insoluble matter by filtration, the reaction mixture was concentrated under reduced pressure, washed with hexane and MeOH, and recrystallized with MeOH to obtain bis[dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl). ) phosphine oxide]tris(hexafluoroacetylacetonato)europium(III) was obtained as a reddish-white solid (344 mg, 65% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.5 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −86.0 (brs). ESIMS (m/z): 1552.1 [M-hfa] ⁺ .

Example 8

Under an argon atmosphere, europium acetate n-hydrate (112 mg as 2.5 hydrate, 0.30 mmol) and tricyclohexylphosphine oxide (178 mg, 0.60 mmol) obtained in Reference Example 8 were mixed with dichloromethane (3.0 mL). and stirred at room temperature for 1 hour. A solution of Hhfa in dichloromethane (1.8 M, 0.5 mL, 0.9 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/methanol to obtain a white solid of bis(trihexylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III) (yield: 271 mg, yield: 66 %). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −71.7 (brs). ESIMS (m/z): 1159.3 [M-hfa] ⁺ .

Example 9

Under an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and tricyclopentylphosphine oxide (153 mg, 0.60 mmol) obtained in Reference Example 9 were mixed with dichloromethane (3.0 mL). and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.50 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 7 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/methanol to obtain a white solid of bis(tricyclopentylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III) (yield: 223 mg, yield: 58%). ). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −77.8 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −69.3 (brs). ESIMS (m/z): 1074.9 [M-hfa] ⁺ .

Example 10

Under an argon atmosphere, europium acetate n-hydrate (73 mg as 2.5 hydrate, 0.19 mmol) and (4'-fluoro-[1,1'-biphenyl]-2-yl) obtained in Reference Example 11 Dicyclohexylphosphine oxide (150 mg, 0.38 mmol) was added with dichloromethane (2.0 mL) and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.32 mL, 0.58 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was concentrated under reduced pressure and recrystallized from dichloromethane/hexane to give bis[(4'-fluoro-[1,1'-biphenyl]-2-yl)dicyclohexylphosphine oxide]tris(hexafluoroacetylacetonato). A white solid of europium (III) was obtained (196 mg, 65% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −78.4 (brs, 18F), −112.8 (brs, 2F). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −80.5 (brs). ESIMS (m/z): 1335.2 [M-hfa] ⁺ .

Example 11

Under an argon atmosphere, europium acetate n-hydrate (66 mg as 2.5 hydrate, 0.18 mmol) and (4'-trifluoromethyl-[1,1'-biphenyl]-2- Dichloromethane (2.0 mL) was added to yl)dicyclohexylphosphine oxide (155 mg, 0.36 mmol) and stirred at room temperature for 1 hour. A 1.0 M dichloromethane solution of Hhfa (0.54 mL, 0.54 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was concentrated under reduced pressure and recrystallized from acetone to give bis[(4'-trifluoromethyl-[1,1'-biphenyl]-2-yl)dicyclohexylphosphine oxide]tris(hexafluoroacetylacetonato). A white solid of europium (III) was obtained (161 mg, 56% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −62.5 (brs, 6F), −78.4 (brs, 18F). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −80.5 (brs). ESIMS (m/z): 1434.2 [M-hfa] ⁺ .

Example 12

Under an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and 3-biphenylyl(dicyclohexyl)phosphine oxide (220 mg, 0.60 mmol) obtained in Reference Example 13 were mixed with dichloromethane (3 .0 mL) was added and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.50 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/methanol to obtain a white solid of bis[3-biphenylyl(dicyclohexyl)phosphine oxide]tris(hexafluoroacetylacetonato)europium (III) (yield: 250 mg, 55% yield). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −78.2 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −79.3 (brs). ESIMS (m/z): 1299.4 [M-hfa] ⁺ .

Example 13

In an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and 4-biphenylyl(dicyclohexyl)phosphine oxide (220 mg, 0.60 mmol) obtained in Reference Example 14 were mixed with dichloromethane (3 .0 mL) was added and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.50 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/hexane to obtain a white solid of bis[(4-biphenylyl(dicyclohexyl)phosphinephosphine oxide]tris(hexafluoroacetylacetonato)europium (III) (yield: 350 mg, yield 77%) ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −78.2 (brs) ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −80.1 (brs).ESIMS (m/z): 1299.4 [M-hfa] ⁺ .

Example 14

Under an argon atmosphere, europium acetate n-hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and dicyclohexyl(2-phenoxyphenyl)phosphine oxide (230 mg, 0.60 mmol) obtained in Reference Example 15 were mixed with dichloromethane ( 3.0 mL) was added and stirred at room temperature for 1 hour. A 1.8 M dichloromethane solution of Hhfa (0.50 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 8 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/methanol to obtain a white solid of bis[dicyclohexyl(2-phenoxyphenyl)phosphine oxide]tris(hexafluoroacetylacetonato)europium (III) (yield: 299 mg). , yield 65%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −78.2 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −78.9 (brs). ESIMS (m/z): 1331.3 [M-hfa] ⁺ .

Example 15

Under an argon atmosphere, diaquatris(hexafluoroacetylacetonato)europium (III) (243 mg, 0.30 mmol) obtained in Reference Example 16 and (2-biphenylyl)dicyclohexylphosphine oxide (220 mg, 0.60 mmol) obtained in Reference Example 1 ) was added with dichloromethane (3.0 mL) and stirred at room temperature for 3 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure and recrystallized with dichloromethane/methanol to give bis[(2-biphenylyl)dicyclohexylphosphine oxide)]tris(hexafluoroacetylacetonato)europium (III). (336 mg, 74% yield).

Example 16

Under an argon atmosphere, diaquatris(hexafluoroacetylacetonato)europium (III) (2.0 g, 2.47 mmol) obtained in Reference Example 16 and tricyclohexylphosphine oxide (1.47 g, 4.94 mmol) obtained in Reference Example 8 Methanol (50.0 mL) was added to and stirred at 65° C. for 3 hours. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure and recrystallized with methanol to obtain a white solid of bis(trihexylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III) (yield: 2 .4 g, 71% yield).

Example 17

Europium acetate n-hydrate (51.6 mg, 0.138 mmol as 2.5 hydrate) and di(1-adamantyl)-2-biphenylphosphine oxide obtained in Reference Example 17 (130 mg, 0.138 mmol) were treated under an argon atmosphere. 276 mmol) was added with dichloromethane (5.0 mL), and the mixture was stirred at room temperature for 1 hour. A solution of Hhfa in dichloromethane (1.8 M, 0.5 mL, 0.9 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure and recrystallized with dichloromethane and hexane to give [di(1-adamantyl)-2-biphenylphosphine oxide]tris(hexafluoroacetylacetonato) europium ( A white solid of III) was obtained (yield 344 mg, yield 65%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ): −79.1 (brs, 18F). ³¹ P-NMR (162 MHz, CDCl ₃ ): −101.8 (brs, 1P). ESIMS (m/z): 1037.4 [M-hfa] ⁺ .

Production example 1
Bis[(2-biphenylyl)dicyclohexylphosphine oxide]tris(hexafluoroacetylacetonate) obtained in Example 1 was added to a toluene solution (4 mL) of ethylene/vinyl acetate copolymer resin (Ultrathene 720) (915 mg) manufactured by Tosoh Corporation. ) A toluene solution (1 mL) of europium (III) (1 mg) was added. This mixture was stirred at room temperature for 30 minutes, the resulting viscous liquid was applied to a flat quartz glass substrate surface by drop casting, and dried at a temperature of 60° C. for 24 hours. An optical material containing phosphine oxide]tris(hexafluoroacetylacetonato)europium(III) was prepared.

Production example 2
To a toluene solution (4 mL) of ethylene/vinyl acetate copolymer resin (Ultrathene 720) (920 mg) manufactured by Tosoh, bis(trihexylphosphine oxide) tris(hexafluoroacetylacetonato) europium ( A toluene solution (1 mL) of III) (1 mg) was added. This mixture was stirred at room temperature for 30 minutes, and the resulting viscous liquid was applied to a flat quartz glass substrate surface by a drop casting method and dried at a temperature of 60°C for 24 hours. An optical material containing tris(hexafluoroacetylacetonato)europium(III) was prepared.

Production example 3
Methyl methacrylate monomer (70. 0 g, 700 mmol), benzoyl peroxide (1.4 g, 5.8 mmol) as a polymerization initiator, and bis(trihexylphosphine oxide) tris(hexafluoroacetylacetonato) europium (III) obtained in Example 8 (70 .4 mg, 0.051 mmol) was added. This mixture was stirred at 65°C for 4 hours, and the resulting white suspension was filtered, washed with pure water, and dried under reduced pressure by heating (80°C, 2 hours). An optical material (66.1 g) containing fluoroacetylacetonato)europium(III) was prepared.

Comparative example 1

Under an argon atmosphere, ethanol (200 mL) was added to diaquatris(hexafluoroacetylacetonato)europium (III) (5.0 g, 6.18 mmol) obtained in Reference Example 16 and triphenylphosphine oxide (3.4 g, 12.4 mmol). was added and stirred at 65° C. for 3 hours. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure and recrystallized with methanol to obtain a white solid of bis(triphenylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III) (yield 4.0%). 8 g, 58% yield). This compound is specifically described in RUB1453869 and JP-A-2003-81986. ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −79.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −91.3 (brs). ESIMS (m/z): 1123.4 [M-hfa] ⁺ .

Comparative example 2

Dichloromethane (3.0 mL) was added to europium acetate n-hydrate (2.5 hydrate, 112 mg, 0.30 mmol) and tributylphosphine oxide (131 mg, 0.60 mmol) under an argon atmosphere, and the mixture was stirred at room temperature for 1 hour. bottom. A 1.8 M dichloromethane solution of Hhfa (0.50 mL, 0.90 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and recrystallized from dichloromethane/hexane to obtain a white solid of bis(tributylphosphine oxide)tris(hexafluoroacetylacetonato)europium (III) (yield: 243 mg, yield: 67%). . ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −78.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −63.0 (brs). ESIMS (m/z): 1003.0 [M-hfa] ⁺ .

Evaluation Examples Emission spectrum measurement of the europium complexes of the present invention and the europium complexes obtained in Comparative Examples 1 and 2, and light resistance evaluation samples were the europium complexes synthesized in Examples 1 to 17 and Comparative Examples 1 and 2. The obtained europium complex powder was pulverized in a mortar to a fine powder, and the powder was filled in a powder cell (PSH-002, manufactured by JASCO Corporation) under a dry air atmosphere.

The measurement results of the emission spectra (excitation light of 380 nm) of the europium complexes obtained in Examples 1 to 17 are shown in FIGS. Measurement results (excitation light of 380 nm) are shown in FIGS. Measurement conditions were an excitation side slit of 1 nm and a fluorescence side slit of 1 nm. Emissions at about 593 nm, 612 nm, 653 nm and 699 nm due to ff electronic transitions characteristic of Eu(III) complexes were observed.

Table 1 shows the evaluation results of the emission quantum yield of the europium complexes obtained in Examples 1 to 14 at an excitation light wavelength of 380 nm.

The light resistance was evaluated by the method shown below. Light resistance evaluation of Examples 1 to 14 and Comparative Examples 1 and 2 was performed by measuring the emission intensity at the maximum emission wavelength around 615 nm with a spectrophotometer (manufactured by JASCO Corporation, FP-6500). Measurement conditions were an excitation side slit of 5 nm, a fluorescence side slit of 5 nm, and an excitation light wavelength of 380 nm. Next, at room temperature, UV light of 200 mW/cm ² (365 nm) was irradiated for a predetermined time (0 to 24 hours) using a UV light irradiator (SP-9, manufactured by Ushio Inc.) and a lens. The luminescence intensity of the sample after UV light irradiation was measured again with a spectrophotometer, and the luminescence intensity retention rate from the initial state was calculated from the following formula. evaluated the sex.

Emission intensity residual ratio (%) (I/I ₀ ) = (emission intensity at maximum emission wavelength after UV irradiation)/(emission intensity at maximum emission wavelength before UV irradiation) × 100
The evaluation results of the light resistance of the europium complexes of the present invention obtained in Examples 1 to 14 are shown in FIGS. 19 to 32 together with the results of Comparative Examples 1 and 2. The rate results are shown in Table 2.

As shown in FIGS. 19 to 32, the europium complex of the present invention has excellent light resistance by introducing a specific substituent on the phosphorus atom, thereby remarkably suppressing the decrease in emission intensity due to UV light irradiation. I understand.

On the other hand, the compound specifically described in RUB1453869 and JP-A-2003-81986 (Comparative Example 1) and the europium complex having a linear alkyl group on the phosphorus atom disclosed in JP-A-2005-223276 ( In Comparative Example 2), the emission intensity is remarkably lowered by UV light irradiation.

The europium complex of the present invention does not attenuate the emission intensity even after long-term light irradiation, compared to a europium complex having triphenylphosphine oxide and a europium complex having a linear alkyl group on the phosphorus atom. It has high photostability. Further, the europium complex of the present invention has high solubility, is easily dissolved in an organic solvent, a polymer material, or the like, and can be uniformly dispersed. Therefore, it is useful as a film for solar cells, a film for agriculture, an LED phosphor, an organic EL material, a light-emitting material such as security ink, and a wavelength conversion material used therefor.

Claims (14)

General formula (1)

[In the formula, R ¹ is a cyclic alkyl group having 3 to 10 carbon atoms, and R ² and R ³ are phenyl groups represented by general formula (2a).

(Wherein, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom; a fluorine atom; an alkyl group having 1 to 3 carbon atoms; an alkyloxy group having 1 to 3 carbon atoms; aryloxy group having 6 to 10 carbon atoms; fluoroalkyl group having 1 to 3 carbon atoms; fluoroalkyloxy group having 1 to 3 carbon atoms; or fluorine atom, alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms represents an alkyloxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group, a hydroxyl group, or a phenyl group which may be substituted with a cyano group). However, the case where R ¹ is a cyclohexyl group and R ² and R ³ are phenyl groups is excluded. ^R4 represents a hydrogen atom, a deuterium atom, or a fluorine atom. W ¹ and W ² each independently represent an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group. n represents an integer of 1 to 3; ] The europium complex represented by. 2. The europium complex according to claim 1, wherein ^R1 in the general formula (1) is a cyclohexyl group. 3. The europium complex according to claim 1, wherein n is 2 in the general formula (1). 4. The europium complex according to any one of claims 1 to 3, wherein in said general formula (1), W ¹ and W ² are each independently a fluoroalkyl group having 1 to 6 carbon atoms. 5. The europium complex according to any one of claims 1 to 4, wherein R ⁴ in the general formula (1) is a hydrogen atom. In general formula (2a), X ¹ , X ² and X ³ are each independently a hydrogen atom, a methyl group, or general formula (2b)

[wherein Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, It is an oxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms or a phenyl group optionally substituted with a fluorine atom. ], and each of X ⁴ and X ⁵ is independently a hydrogen atom or a methyl group. General formula (1)

[In the formula, R ¹ and R ² are each independently a cyclic alkyl group having 3 to 10 carbon atoms, and R ³ is a cyclic alkyl group having 3 to 10 carbon atoms or a phenyl group represented by general formula (2a).

(Wherein, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom; a fluorine atom; an alkyl group having 1 to 3 carbon atoms; an alkyloxy group having 1 to 3 carbon atoms; aryloxy group having 6 to 10 carbon atoms; fluoroalkyl group having 1 to 3 carbon atoms; fluoroalkyloxy group having 1 to 3 carbon atoms; or fluorine atom, alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms represents an alkyloxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms, a fluorophenyl group, a hydroxyl group, or a phenyl group which may be substituted with a cyano group). ^R4 represents a hydrogen atom, a deuterium atom, or a fluorine atom. W ¹ and W ² each independently represent an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group. n represents an integer of 1 to 3; ] The europium complex represented by. 8. The europium complex according to claim 7, wherein R ³ in the general formula (1) is a cyclic alkyl group having 3 to 10 carbon atoms. The europium complex according to claim 7 or 8, wherein R ¹ , R ² and R ³ in the general formula (1) are cyclohexyl groups. The europium complex according to any one of claims 7 to 9, wherein n is 2 in the general formula (1). 11. The europium complex according to any one of claims 7 to 10, wherein in said general formula (1), W ¹ and W ² are each independently a fluoroalkyl group having 1 to 6 carbon atoms. The europium complex according to any one of claims 7 to 11, wherein R ⁴ in general formula (1) is a hydrogen atom. In general formula (2a), X ¹ , X ² and X ³ are each independently a hydrogen atom, a methyl group, or general formula (2b)

[wherein Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, It is an oxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms or a phenyl group optionally substituted with a fluorine atom. ], and X ⁴ and X ⁵ are each independently a hydrogen atom or a methyl group, the europium complex according to any one of claims 7 to 12. 14. The europium complex according to any one of claims 7 to 13, wherein the europium complex is represented by the following formulas 1-1 to 1-11 and 1-19 to 1-21.

[In the formula, Cy represents a cyclohexyl group. ]

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