JP7576540B2 - Luminescent europium complexes - Google Patents

Description

The present invention relates to a luminescent europium complex that has high absorption ability for long-wavelength ultraviolet radiation and high solubility.

Optoelectronics such as optical communications and displays, and the energy industry including solar cells, are core technologies of the next generation, and various inorganic glass materials, ceramic materials, laser materials, organic low-molecular-weight luminescent materials, wavelength conversion materials, etc. are being created for use in these technologies.

Wavelength conversion materials are materials that absorb light of a specific wavelength and emit light of another wavelength. They can be used as optical materials by adding them to resin materials. In particular, wavelength conversion materials with high solubility can be added to resin materials in high concentrations. Optical materials containing wavelength conversion materials in high concentrations can reduce the amount of resin material required to obtain the desired light intensity, making it possible to make optical materials thinner, which is expected to improve productivity by shortening the drying process and reduce the size of optical materials. In addition, wavelength conversion materials with high long-wavelength ultraviolet absorption can be used as a substitute for ultraviolet absorbers to suppress photodegradation of resins and devices due to exposure to ultraviolet rays.

In recent years, europium complexes with β-diketonato ligands and phenanthroline ligands, which are strong luminescent rare earth metal complexes, have been reported as such wavelength conversion materials (Non-Patent Document 1) and europium complexes with β-diketonato ligands and phosphine oxide ligands (Patent Documents 1 and 2). However, the europium complexes described in Patent Documents 1 and 2 have low absorption ability for long-wavelength ultraviolet light.

Furthermore, although the europium complexes disclosed in Patent Document 3, Patent Document 4, Non-Patent Document 2, Non-Patent Document 3, and Non-Patent Document 4 are similar to the europium complex described in the present application, there is no description whatsoever regarding the solubility of these complexes. Patent Document 5 and Non-Patent Document 5 disclose europium complexes having linear alkylphosphine oxide ligands as highly soluble europium complexes, but these are highly amorphous and therefore difficult to recrystallize in the production process, and it is difficult to produce these europium complexes at high purity.
Therefore, there is a need for wavelength converting materials that have high long wavelength ultraviolet absorption capacity and that are luminescent europium complexes that have high solubility.

RUB1453860 Japanese Patent Publication No. 2003-81986 Japanese Patent Publication No. 2005-223276 Japanese Patent Publication No. 2014-197144 Japanese Patent Publication No. 2008-159604

Chemical Communications, No. 43, p. 6649 (2009) Abstracts of the 36th Inorganic Polymer Research Symposium, Society of Polymer Science, 2017, p. 47 Abstracts of the 98th Annual Meeting of the Chemical Society of Japan (2018), Chemical Society of Japan, 2PA-194 European Journal of Inorganic Chemistry, No. 3, p. 639 (2017) Japanese Journal of Applied Physics, Vol. 45, p. 558 (2006)

The object of the present invention is to provide a luminescent europium complex that has high absorption ability for long-wavelength ultraviolet radiation and high solubility.

As a result of extensive research into solving the above problems, the inventors discovered that europium complexes incorporating specific ligands have high absorption ability for long-wavelength ultraviolet light and are highly soluble in solvents and resin materials, thus completing the present invention.

（式中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、炭素数３～１０の環状第二級アルキル基又は下記式（２）で表されるフェニル基を表す。但し、Ｒ^１、Ｒ^２及びＲ^３は同時にフェニル基とならず、Ｒ^１、Ｒ^２及びＲ^３の内１つがシクロヘキシル基、２つがフェニル基とはならない。Ｗ^１及びＷ^２は、各々独立に、炭素数１～６のフルオロアルキル基、フェニル基、２－チエニル基又は３－チエニル基を表す。）

（式中、Ｘ^１は水素原子；炭素数１～３のアルキル基；炭素数１～３のアルキルオキシ基；炭素数１～３のフルオロアルキル基又はフッ素原子、炭素数１～３のアルキル基、炭素数１～３のアルキルオキシ基若しくは炭素数１～３のフルオロアルキル基で置換されてもよいフェニル基を表す。） That is, the gist of the present invention is a europium complex represented by the following formula (1) (hereinafter, also referred to as europium complex (1)).

(In the formula, R ¹ , R ² and R ³ each independently represent a cyclic secondary alkyl group having 3 to 10 carbon atoms or a phenyl group represented by the following formula (2); however, R ¹ , R ² and R ³ are not all phenyl groups at the same time, and one of R ¹ , R ² and R ³ is not a cyclohexyl group and two are not phenyl groups. ^{W 1} and W ² each independently represent a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group.)

(In the formula, ^X1 represents a hydrogen 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 phenyl group which 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, or a fluoroalkyl group having 1 to 3 carbon atoms.)

The europium complex (1) according to the present invention is highly soluble in solvents and resin materials, and can be uniformly dispersed. In addition, because it has a high ability to absorb long-wavelength ultraviolet light, it can be used as a substitute for ultraviolet absorbers to suppress photodegradation of resins and devices due to exposure to ultraviolet light.

1 shows the excitation and emission spectra of the europium complex (1-1) obtained in Example 1. 1 shows the excitation and emission spectra of the europium complex (1-2) obtained in Example 2. 1 shows the excitation and emission spectra of the europium complex (1-3) obtained in Example 3. 1 shows the excitation and emission spectra of the europium complex (1-5) obtained in Example 5. 1 shows the excitation and emission spectra of the europium complex (1-6) obtained in Example 6.

1 shows the excitation and emission spectra of the europium complex (1-7) obtained in Example 7. 1 shows the excitation and emission spectra of the europium complex (1-8) obtained in Example 8. 1 shows the excitation and emission spectra of the europium complex (1-9) obtained in Example 10. 1 shows the excitation and emission spectra of the europium complex (1-10) obtained in Example 11. 1 shows the excitation and emission spectra of the europium complex (1-11) obtained in Example 12.

1 shows the excitation and emission spectra of the europium complex (1-13) obtained in Example 14. 1 shows the excitation and emission spectra of the europium complex (1-15) obtained in Example 15. 1 shows the excitation and emission spectra of the europium complex (1-16) obtained in Example 16. 1 shows the excitation and emission spectra of the europium complex (1-20) obtained in Example 17. 1 shows the excitation and emission spectra of the europium complex (1-22) obtained in Example 18.

1 shows the excitation and emission spectra of the europium complex (1-23) obtained in Example 19. 1 shows the excitation and emission spectra of the europium complex (1-25) obtained in Example 20. 2 shows the excitation and emission spectra of the europium complex (1-26) obtained in Example 21. 2 shows the excitation and emission spectra of the europium complex (1-28) obtained in Example 23.

1 shows UV-Vis spectra of the europium complex (1-1) obtained in Example 1 and the europium complex obtained in Comparative Example 2. 1 is a UV-Vis spectrum of the europium complex (1-2) obtained in Example 2. 1 is a UV-Vis spectrum of the europium complex (1-6) obtained in Example 6. 1 is a UV-Vis spectrum of the europium complex (1-9) obtained in Example 10. 1 is a UV-Vis spectrum of the europium complex (1-13) obtained in Example 13.

(Europium complex (1))
The definitions of R ¹ , R ² , R ³ , X ¹ , W ¹ and W ² in the formula (1) representing the europium complex (1) of the present invention will be explained.
Specific examples of the cyclic secondary alkyl group having 3 to 10 carbon atoms represented by R ¹ , R ² , and R ³ in formula (1) include a cyclopropyl group, a 2,3-dimethylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, a bicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-2-yl group, and an adamantan-2-yl group. In view of cost, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, and the like are preferred, and a cyclohexyl group is more preferred.

The alkyl group having 1 to 3 carbon atoms represented by ^X1 in formula (2) may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a 1-methylethyl group.
The alkyloxy group having 1 to 3 carbon atoms represented by X ¹ in formula (2) may be either a linear or branched alkyloxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a 1-methylethyloxy group.

The fluoroalkyl group having 1 to 3 carbon atoms represented by X ¹ in formula (2) may be either a linear or branched fluoroalkyl group, and examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl group, and a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

When X ¹ in formula (2) is a phenyl group, the phenyl group may be a phenyl group substituted with at least one selected from the group consisting of a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, and a fluoroalkyl group having 1 to 3 carbon atoms (hereinafter, also referred to as a substituted phenyl group). Examples of the substituted phenyl group include a 2-fluorophenyl group, a 2-methylphenyl group, a 2-methoxyphenyl group, and a 2-(trifluoromethyl)phenyl group.

As X ¹ in formula (2), from the viewpoint of inexpensiveness, a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a methoxy group, a 1-methylethyloxy group, a phenyl group which may be substituted with an alkyl group having 1 to 3 carbon atoms, a phenyl group which may be substituted with an alkyloxy group having 1 to 3 carbon atoms, a phenyl group which may be substituted with a fluorine atom, or a phenyl group which may be substituted with a linear fluoroalkyl group is more preferable, and a hydrogen atom, a methyl group, or a phenyl group is more preferable.

R ¹ , R ² and R ³ in formula (1) are preferably a cyclohexyl group or a phenyl group represented by formula (2), and particularly preferably a cyclohexyl group, a 2-biphenyl group or a 2-methylphenyl group.

The fluoroalkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in formula (1) may be any of linear, branched, and cyclic. Specifically, the fluoroalkyl group may be a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 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, Examples of such groups include a 2,2,3,3,4,4,4-heptafluoro-1,1-bis(trifluoromethyl)butyl group, a 1,2,3,3,4,4,4-heptafluoro-1,2-bis(trifluoromethyl)butyl group, a 1,2,2,3,4,4,4-heptafluoro-1,3-bis(trifluoromethyl)butyl group, a 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl group, a 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, a 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group, a perfluorocyclohexyl group, and a perfluorocyclopentylmethyl group.

In terms of high solubility, W ¹ and W ² in formula (1) are preferably a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group, or a 3-thienyl group, and more preferably a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a phenyl group, a 2-thienyl group, or a 3-thienyl group.

Specific examples of the europium complex (1) include structures represented by any of the following (1-1) to (1-29), but the present invention is not limited to these.
In this specification, Ph represents a phenyl group, Cy represents a cyclohexyl group, and Me represents a methyl group.

Among the above formulas (1-1) to (1-29), the compounds represented by formulas (1-1) to (1-11), (1-13), (1-15), (1-16) or (1-20) are preferred in terms of high production yield, the compounds represented by formulas (1-1) to (1-4), (1-6), (1-8) to (1-11), (1-13), (1-15), (1-16) or (1-20) are even more preferred in terms of ease of synthesis, the compounds represented by formulas (1-1), (1-2), (1-6), (1-8), (1-9) or (1-13) are even more preferred in terms of easy availability of raw materials, and the compounds represented by formulas (1-8), (1-9) or (1-13) are especially preferred in terms of particularly high solubility.

(Method for producing europium complex (1))
Next, a method for producing the europium complex (1) (hereinafter referred to as the production method of the present invention) will be described.
(Production method 1)
An example of a method for producing europium complex (1) is production method 1 (hereinafter also referred to as method 1), which comprises reacting a phosphine oxide represented by formula (4) (hereinafter referred to as phosphine oxide (4)), a β-diketone represented by formula (3) (hereinafter referred to as β-diketone (3)), and a europium salt.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｗ^１及びＷ^２は、式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｗ^１及びＷ^２と同じ意味を表す。）

(In the formula, R ¹ , R ² , R ³ , W ¹ and W ² have the same meanings as R ¹ , R ² , R ³ , W ¹ and W ² in formula (1).)

In Method 1, specific examples of the cyclic secondary alkyl group having 3 to 10 carbon atoms represented by R ¹ , R ^2, and R ³ in Formula (4) include a cyclopropyl group, a 2,3-dimethylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethylcyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecanyl group, a bicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-2-yl group, and an adamantan-2-yl group.

When R ¹ , R ² and R ³ in formula (4) are represented by formula (2), the alkyl group having 1 to 3 carbon atoms for X ¹ may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a 1-methylethyl group.
When R ¹ , R ² and R ³ in formula (4) are represented by formula (2), the alkyloxy group having 1 to 3 carbon atoms for X ¹ may be either a linear or branched alkyloxy group, and examples thereof include a methoxy group, an ethyloxy group, a propyloxy group and a 1-methylethyloxy group.

When R ¹ , R ² and R ³ in formula (4) are represented by formula (2), the fluoroalkyl group having 1 to 3 carbon atoms for X ¹ may be any of a linear or branched fluoroalkyl group, and examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a 1,1,1,2,3,3,3-hexafluoro-2-propyl group and a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

When R ¹ , R ² and R ³ in formula (4) are represented by formula (2), the phenyl group of X ¹ may be a substituted phenyl group substituted with at least one selected from the group consisting of a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, and a fluoroalkyl group having 1 to 3 carbon atoms. Examples of the substituted phenyl group include a 2-fluorophenyl group, a 2-methylphenyl group, a 2-methoxyphenyl group, a 2-phenoxyphenyl group, and a 2-(trifluoromethyl)phenyl group.

When R ¹ , R ² and R ³ in formula (4) are represented by formula (2), the substituent represented by X ¹ is preferably a fluorine atom, an alkyl group having 1 to 3 carbon atoms, a methoxy group, a 1-methylethyloxy group, a phenyl group which may be substituted with an alkyl group having 1 to 3 carbon atoms, a phenyl group which may be substituted with an alkyloxy group having 1 to 3 carbon atoms, a phenyl group which may be substituted with a fluorine atom or a phenyl group which may be substituted with a linear fluoroalkyl group, in terms of cost. A methyl group, a 1-methylethyl group, a methoxy group and a 1-methylethyloxy group are more preferable.

The phosphine oxide (4) used in Method 1 can be obtained by the method described in Chemical Reviews, Vol. 60, pp. 243-260, 1960, or the like.
Specific examples of the phosphine oxide (4) used in the method 1 include those represented by the following formulas (4-1) to (4-11), but are not limited thereto.

Among the compounds represented by the above formulas (4-1) to (4-11), the compounds represented by the formulas (4-1) to (4-3) or (4-7) are preferred as the phosphine oxide (4) because of their good reaction yield.

In the method 1, the fluoroalkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in the formula (3) may be any of linear, branched, and cyclic. Specifically, the fluoroalkyl group may be a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 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, Examples of such groups include a 2,2,3,3,4,4,4-heptafluoro-1,1-bis(trifluoromethyl)butyl group, a 1,2,3,3,4,4,4-heptafluoro-1,2-bis(trifluoromethyl)butyl group, a 1,2,2,3,4,4,4-heptafluoro-1,3-bis(trifluoromethyl)butyl group, a 1,1,3,3,4,4,4-heptafluoro-2,2-bis(trifluoromethyl)butyl group, a 1,2,2,3,4,4,4-heptafluoro-2,3-bis(trifluoromethyl)butyl group, a 1,1,2,2,4,4,4-heptafluoro-3,3-bis(trifluoromethyl)butyl group, a perfluorocyclohexyl group, and a perfluorocyclopentylmethyl group.

In method 1, as the substituents represented by W ¹ and W ² in formula (3), a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, or a thienyl group is preferable, from the viewpoint of good solubility, and a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a phenyl group, or a thienyl group is more preferable.

Specific examples of the β-diketone (3) used in method 1 include 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione, 4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedione, 1,3-di-(2-thienyl)-1,3-propanedione, and 1,3-diphenyl-1,3- Examples of such compounds include propanedione, 1-phenyl-3-(2-thienyl)-1,3-propanedione, 4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedione, 1,3-di-(3-thienyl)-1,3-propanedione, 1-(2-thienyl)-3-(3-thienyl)-1,3-propanedione, 4,4,5,5,6,6,6-heptafluoro-1-(3-thienyl)-1,3-hexanedione, and 1-phenyl-3-(3-thienyl)-1,3-propanedione.

The β-diketone (3) used in Method 1 can be obtained, for example, by the method described in Journal of the American Chemical Society, Vol. 66, pp. 1220-1222, 1944. Alternatively, a commercially available product may be used.
The β-diketone (3) has an active hydrogen atom, and becomes an anionic ligand upon loss of a hydrogen ion.

β-diketone (3) can undergo isomerization to form enol (3a) or enol (3b), and β-diketone (3) includes either enol. In this specification, β-diketone (3) is represented by formula (3). Similarly, europium complex (1) can undergo isomerization to form europium complex (1a), and europium complex (1) includes europium complex (1a). In this specification, europium complex (1) is represented by formula (1).

The europium salts used in Method 1 include, for example, halide salts such as europium (III) fluoride, europium (III) chloride, europium (III) bromide, and europium (III) iodide, or hydrates thereof; organic acid salts such as europium (III) oxalate, europium (III) acetate, europium (III) trifluoroacetate, and europium (III) trifluoromethanesulfonate, or Examples of suitable salts include hydrates thereof; metal alkoxides such as tris[N,N-bis(trimethylsilyl)amide]europium(III), europium(III) trimethoxide, europium(III) triethoxide, and europium(III) tri(2-propoxide); and inorganic acid salts such as europium(III) phosphate, europium(III) sulfate, and europium(III) nitrate, or hydrates thereof. Among these, in terms of good reaction yield, europium(III) chloride, europium(III) nitrate, or organic acid salts such as europium(III) oxalate, europium(III) acetate, europium(III) trifluoroacetate, and europium(III) trifluoromethanesulfonate are preferred, with europium(III) acetate, europium(III) chloride, and europium(III) nitrate being more preferred.

In method 1, it is preferable to carry out the reaction in a solvent because the reaction yield of europium complex (1) is good. There are no particular limitations on the type of solvent that can be used as long as it does not inhibit the reaction. Examples of solvents that can be used include halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, alcohols such as methanol, ethanol, propanol, and 1-methylethyl 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, and ethylene glycol monobutyl ether, ethers such as diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, tetrahydrofuran, and cyclopentyl methyl ether, ketones such as tert-butyl methyl ketone, 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. These solvents may be used alone or in combination in any ratio. Dichloromethane, chloroform, methanol or ethanol is preferred as the solvent in terms of the high reaction yield of the europium complex (1).

Next, the molar ratio of europium salt and phosphine oxide (4) in method 1 will be described. It is preferable to use 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol, of phosphine oxide (4) per mol of europium salt.
The molar ratio of europium salt and β-diketone (3) in method 1 will be described below. It is preferable to use 1.0 to 10 moles, more preferably 2.0 to 8.0 moles of β-diketone (3) per mole of europium salt.

In the method 1, the reaction temperature and reaction time are not particularly limited, and general conditions used by those skilled in the art when producing metal complexes can be used. As a specific example, europium complex (1) can be produced in a good yield by selecting a reaction temperature of -80°C to 120°C and a reaction time of 1 minute to 120 hours.
The europium complex (1) produced by the method 1 can be purified by a purification method generally used by those skilled in the art for purifying metal complexes, which can be appropriately selected and used. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography, etc.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｗ^１及びＷ^２は式（１）のＲ^１、Ｒ^２、Ｒ^３、Ｗ^１及びＷ^２と同じ意味を表す。Ｑは配位分子を表す。ｍは０～３の整数を表す。） (Production method 2)
As a method for producing the europium complex (1) of the present invention, there can also be mentioned a production method 2 (hereinafter also referred to as method 2) in which a diketonato complex (5) represented by the following formula (5) is reacted with a phosphine oxide (4) represented by the following formula (5).

(In the formula, R ¹ , R ² , R ³ , W ¹ and W ² have the same meanings as R ¹ , R ² , R ³ , W ¹ and W ² in formula (1). Q represents a coordination molecule. m represents an integer of 0 to 3.)

In method 2, specific examples of the coordinating molecule represented by Q include water, heavy water, tetrahydrofuran, pyridine, imidazole, acetone, methanol, ethanol, propanol, and 1-methylethyl alcohol, as well as nitriles such as acetonitrile and propionitrile, amines such as ammonia, diethylamine and triethylamine, and ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran. Of these, water is preferred in terms of ease of synthesis of the diketonato complex (5).
In the diketonato complex (5), m represents an integer of 0 to 3, and is preferably 2 in terms of ease of synthesis.

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

Specific examples of the diketonato complex (5) used in method 2 include tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)europium(III), tris[4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato]europium(III), tris(4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedionato)europium(III), tris[1,3-di-(2-thienyl)-1,3-propanedionato]europium(III), tris(1,3-diphenyl- 1,3-propanedionato)europium(III), tris[1-phenyl-3-(2-thienyl)-1,3-propanedionato]europium(III), tris[4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedionato]europium(III), tris[4,4,5,5,6,6,6-heptafluoro-1-(3-thienyl)-1,3-hexanedionato]europium(III), tris[1-(2-thienyl)-3-(3-thienyl)-1,3-propanedionato]europium(III), tris[1-phenyl-3-(3-thienyl)-1,3-propanedionato]europium(III), or hydrates thereof, and the like can be exemplified.

The phosphine oxide (4) used in Method 2 can be obtained by the method described in Reference Example 3 described later, Chemical Reviews, Vol. 60, pp. 243-260, 1960, and Organic Letters, Vol. 13, pp. 3478-3481, 2011, or the like.
As the phosphine oxide (4) used in the method 2, the same ones as those exemplified in the explanation of the above method 1 can be exemplified.

In method 2, it is preferable to carry out the reaction in a solvent because the reaction yield of europium complex (1) is good. There are no particular limitations on the type of solvent that can be used as long as it does not inhibit the reaction. Examples of solvents that can be used include halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene; alcohols such as methanol, ethanol, propanol, and 1-methylethyl 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 diethyl ether, tert-butyl methyl ether, 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; hydrocarbons such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, and xylene, or water. These solvents can be used alone or in a mixture of two or more in any ratio. As the solvent, dichloromethane, chloroform, methanol or ethanol is preferred in terms of a good reaction yield of the europium complex (1).

Next, the molar ratio of the diketonato complex (5) and the phosphine oxide (4) when carrying out the method 2 will be described. It is preferable to use 0.5 to 5.0 moles, more preferably 1.0 to 3.0 moles, of the phosphine oxide (4) per mole of the diketonato complex (5).
In Method 2, the reaction temperature and reaction time are not particularly limited, and general conditions used by those skilled in the art when producing metal complexes can be used. As a specific example, europium complex (1) can be produced in a good reaction yield by selecting a reaction temperature of -80°C to 120°C and a reaction time of 1 minute to 120 hours.
The europium complex (1) produced by the method 2 can be purified by a purification method generally used by those skilled in the art for purifying metal complexes, which can be appropriately selected and used. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography, etc.
The diketonato complex (5) also undergoes isomerization similar to that of the europium complex (1). In this specification, the diketonato complex (5) is represented by the formula (5).

(Characteristics of europium complex (1))
The europium complex (1) of the present invention is highly soluble, easily dissolved in solvents, resin materials, etc., can be uniformly dispersed, and has a high ability to absorb long wavelength ultraviolet light, particularly ultraviolet light having a wavelength of 320 to 400 nm, and further 360 to 400 nm. Therefore, the europium complex (1) is useful as an optical material, and examples of the optical material that contains the europium complex (1) include light-emitting materials such as solar cell films, agricultural films, LED phosphors, organic EL materials, and security inks, as well as wavelength conversion materials used therein.

In addition, the europium complex (1) of the present invention can be used as an optical material containing one or more selected from a resin material, inorganic glass, and an organic low molecular weight material, and since it has high dispersibility, it is particularly preferable to use it as an optical material containing a resin material. Examples of the resin material include polymethacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, fluorine-containing polymethyl methacrylate, fluorine-containing polyethyl methacrylate, fluorine-containing polypropyl methacrylate, fluorine-containing polyisopropyl methacrylate, fluorine-containing polybutyl methacrylate, fluorine-containing polysec-butyl methacrylate, fluorine-containing polyisobutyl methacrylate, and fluorine-containing polytert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, and polyisobutyl acrylate. Examples of the polyacrylate include polyacrylates such as polytert-butyl acrylate, fluorine-containing polymethyl acrylate, fluorine-containing polyethyl acrylate, fluorine-containing polypropyl acrylate, fluorine-containing polyisopropyl acrylate, fluorine-containing polybutyl acrylate, fluorine-containing polysec-butyl acrylate, fluorine-containing polyisobutyl acrylate, and fluorine-containing polytert-butyl acrylate; polystyrene, polyethylene, polypropylene, polybutene, fluorine-containing polyethylene, fluorine-containing polypropylene, and fluorine-containing polybutene; polyolefins such as polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride, or copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin, and silicone resin.

Among them, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polysec-butyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polysec-butyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof are preferred. Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or copolymers thereof are particularly preferred. These may be used alone or in combination of two or more.
The content of europium complex (1) in the optical material of the present invention containing the europium complex (1) and a resin material is preferably 0.001 to 99% by weight, more preferably 0.01 to 50% by weight.

The inorganic glass may be any glass commonly used by those skilled in the art, such as soda glass, crystal glass, borosilicate glass, and the like.
The organic low molecular weight material may be any material commonly used by those skilled in the art, for example, ionic liquids such as amyltriethylammonium bis(trifluoromethanesulfonyl)imide and tetraamylammonium chloride, and hydrocarbons such as pentadecane, hexadecane, octadecane, nonadecane, icosane, and paraffin.

Methods for obtaining an optical material containing the europium complex (1) of the present invention include a method of using europium complex (1) alone to produce an optical material, a method of incorporating europium complex (1) into an optical material containing one or more selected from a resin material, an inorganic glass, and an organic low molecular weight material to produce an optical material, a method of mixing europium complex (1) with a monomer corresponding to the polymerization of the resin material and polymerizing the monomer to produce an optical material, and a method of dissolving and dispersing the europium complex (1) in a solvent to produce an optical material.

When the europium complex (1) of the present invention is dissolved or dispersed in a solvent to prepare an optical material, examples of the solvent that can be used 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 ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; ethers such as diethyl ether, tert-butyl methyl ether, 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; hydrocarbons such as hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, and xylene, and water. These solvents can be used alone or in a mixture of two or more in any ratio.

The present invention will be explained in more detail below with reference to examples, comparative examples and evaluation examples, but the present invention should not be construed as being limited to these.

The europium complex (1) was identified by the following analytical method.
¹ H-NMR, ¹⁹ F-NMR and ³¹ P-NMR were measured using ULTRASHIELD PLUS AVANCE III (400 MHz, 376 MHz and 162 MHz) and ASCEND AVANCE III HD (400 MHz, 376 MHz and 162 MHz) manufactured by BRUKER. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) as the measurement solvent and tetramethylsilane (TMS) as the internal standard. ¹⁹ F-NMR was measured using deuterated chloroform (CDCl ₃ ), deuterated dimethylsulfoxide (DMSO-d ₆ ) and deuterated acetone (Acetone-d ₆ ) as the measurement solvent. ³¹ P-NMR was measured using deuterated chloroform (CDCl ₃ ).

Mass spectrometry was performed using a Waters 2695-micromass ZQ4000 manufactured by Waters Corporation.
The excitation and emission spectra were measured using a spectrophotometer (JASCO Corporation, FP-6500).
The UV-Vis spectrum was measured using an ultraviolet, visible and near infrared spectrophotometer (V-670, manufactured by JASCO Corporation).
The emission quantum yield was measured using an absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics, C9920-03).
The thermal decomposition temperature was measured using a differential scanning calorimeter (EX STAR 7020, manufactured by SII Nano Technologies).
The reagents used were commercially available.

４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオン（９９９ｍｇ，４．５０ｍｍｏｌ）にエタノール（２０ｍＬ）と１Ｍの水酸化ナトリウム水溶液（４．５ｍＬ，４．５ｍｍｏｌ）を加えた。この混合物に塩化ユウロピウム六水和物（５５０ｍｇ，１．５０ｍｍｏｌ）を加え、室温で３０分間撹拌した。この反応液に水（１５０ｍＬ）を加え、６０℃でさらに３０分間撹拌した。生じた固体をろ取し、水で洗浄することで、ジアクアトリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）の白色固体を得た（収量６９５ｍｇ，収率５４％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＤＭＳＯ－ｄ_６）δ（ｐｐｍ）：－７８．４（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：８３９．１［Ｍ＋Ｎａ］^＋。 (Reference Example 1)

Ethanol (20 mL) and 1M aqueous sodium hydroxide solution (4.5 mL, 4.5 mmol) were added to 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (999 mg, 4.50 mmol). Europium chloride hexahydrate (550 mg, 1.50 mmol) was added to this mixture, and the mixture was stirred at room temperature for 30 minutes. Water (150 mL) was added to the reaction solution, and the mixture was stirred at 60° C. for another 30 minutes. The resulting solid was collected by filtration and washed with water to obtain a white solid of diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (yield 695 mg, 54%). ¹⁹ F-NMR (376 MHz, DMSO-d ₆ ) δ (ppm): −78.4 (brs). ESIMS (m/z): 839.1 [M+Na] ⁺ .

４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオン（９７３ｍｇ，４．５０ｍｍｏｌ）にエタノール（２０ｍＬ）と１Ｍの水酸化ナトリウム水溶液（４．５ｍＬ，４．５ｍｍｏｌ）を加えた。この混合物に塩化ユウロピウム六水和物（５５０ｍｇ，１．５０ｍｍｏｌ）を加え、室温で３０分間撹拌した。この反応液に水（１５０ｍＬ）を加え、６０℃でさらに３０分間撹拌した。生じた固体をろ取し、水で洗浄することで、ジアクアトリス（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）の白色固体を得た（収量１．１７ｇ，収率９８％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＤＭＳＯ－ｄ_６）δ（ｐｐｍ）：－７８．３（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：８２１．２［Ｍ＋Ｎａ］^＋。 (Reference Example 2)

Ethanol (20 mL) and 1M aqueous sodium hydroxide solution (4.5 mL, 4.5 mmol) were added to 4,4,4-trifluoro-1-phenyl-1,3-butanedione (973 mg, 4.50 mmol). Europium chloride hexahydrate (550 mg, 1.50 mmol) was added to this mixture, and the mixture was stirred at room temperature for 30 minutes. Water (150 mL) was added to the reaction solution, and the mixture was stirred at 60° C. for another 30 minutes. The resulting solid was filtered and washed with water to obtain a white solid of diaquatris(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)europium(III) (yield: 1.17 g, 98%). ¹⁹ F-NMR (376 MHz, DMSO-d ₆ ) δ (ppm): −78.3 (brs). ESIMS (m/z): 821.2 [M+Na] ⁺ .

トリシクロヘキシルホスフィン（１．６６ｇ，５．９ｍｍｏｌ）をジクロロメタン（１０ｍＬに溶解し、３０％過酸化水素水（３．０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に水（１５ｍＬ）を入れ、有機層を分離後、水層にクロロホルム（１５ｍＬ）を加え、クロロホルム層を分離した。この操作を２回繰り返した。有機層を併せ、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：クロロホルム／メタノール）により精製することで、トリシクロヘキシルホスフィンオキシドの白色固体を得た（収量１．２４ｇ，収率７１％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：１．９４～１．７３（ｍ，１８Ｈ），１．４８～１．２５（ｍ，１５Ｈ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：５０．０（ｓ）。 (Reference Example 3)

Tricyclohexylphosphine (1.66 g, 5.9 mmol) was dissolved in dichloromethane (10 mL), 30% hydrogen peroxide solution (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, and 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 tricyclohexylphosphine oxide (yield: 1.24 g, 71%). ¹ H-NMR (400 MHz, 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).

トリ（ｏ－トリル）ホスフィン（２５．３ｇ，８３．１ｍｍｏｌ）をジクロロメタン（２００ｍＬ）に溶解し、０℃で３０％過酸化水素水（２８ｍＬ）をゆっくり加え、０℃で２時間撹拌した。反応混合物に水（１００ｍＬ）を入れ、有機層を分離後、水層にクロロホルム（８０ｍＬ）を加え、クロロホルム層を分離した。この操作を２回繰り返した。有機層を併せ、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：クロロホルム／メタノール）により精製することで、トリ（ｏ－トリル）ホスフィンオキシドの白色固体を得た（収量２８．９ｇ，収率＞９９％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：７．４３（ｂｒｄｄ，Ｊ＝７．５，７．４Ｈｚ，３Ｈ），７．３２（ｂｒｄｄ，Ｊ＝７．５，４．１Ｈｚ，３Ｈ），７．１９～７．０５（ｍ，６Ｈ），２．５０（ｓ，９Ｈ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：３７．１（ｓ）。 (Reference Example 4)

Tri(o-tolyl)phosphine (25.3 g, 83.1 mmol) was dissolved in dichloromethane (200 mL), and 30% hydrogen peroxide solution (28 mL) was slowly added at 0° C., followed by stirring at 0° C. for 2 hours. Water (100 mL) was added to the reaction mixture, and the organic layer was separated. Chloroform (80 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 tri(o-tolyl)phosphine oxide (yield 28.9 g, yield >99%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.43 (brdd, J=7.5, 7.4 Hz, 3H), 7.32 (brdd, J=7.5, 4.1 Hz, 3H), 7.19-7.05 (m, 6H), 2.50 (s, 9H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 37.1 (s).

２－（ビフェニル）ジフェニルホスフィン（２．２１ｇ，６．５４ｍｍｏｌ）をジクロロメタン（３０ｍＬ）に溶解し、０℃で３０％過酸化水溶液（１．８ｍＬ）を加え、室温で５時間撹拌した。反応混合物に水（３０ｍＬ）を入れ、有機層を分離後、水層にクロロホルム（３０ｍＬ）を加え、クロロホルム層を分離した。この操作を２回繰り返した。有機層を併せ、硫酸マグネシウムで乾燥後、減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（溶離液：クロロホルム／メタノール）により精製することで、２－（ビフェニル）ジフェニルホスフィンオキシドの白色固体を得た（収量２．８９ｇ，収率＞９９％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：７．６１～７．５２（ｍ，５Ｈ），７．４５～７．２７（ｍ，９Ｈ），７．２３～７．１９（ｍ，２Ｈ），７．０９～７．０１（ｍ，３Ｈ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：２７．７（ｓ）。 (Reference Example 5)

2-(biphenyl)diphenylphosphine (2.21 g, 6.54 mmol) was dissolved in dichloromethane (30 mL), and 30% aqueous peroxide solution (1.8 mL) was added at 0° C., followed by stirring at room temperature for 5 hours. Water (30 mL) was added to the reaction mixture, and the organic layer was separated. Chloroform (30 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 obtained crude product was purified by column chromatography (eluent: chloroform/methanol) to obtain a white solid of 2-(biphenyl)diphenylphosphine oxide (yield 2.89 g, yield >99%). ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.61-7.52 (m, 5H), 7.45-7.27 (m, 9H), 7.23-7.19 (m, 2H), 7.09-7.01 (m, 3H). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): 27.7 (s).

アセトフェノン（３．５ｍＬ，３０．０ｍｍｏｌ）をエタノール（１６．６ｍＬ）に溶解し、１０重量％ナトリウムエトキシドのエタノール溶液（１３．４ｍＬ，３６ｍｍｏｌ）とヘプタフルオロ酪酸エチル（５．２ｍＬ，３０．０ｍｍｏｌ）を加え、加熱還流下に２１時間撹拌した。反応混合物を０℃に冷却後、１０％硫酸を入れて酸性にした後、水層をジエチルエーテルで３回抽出した。有機層を併せ、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物を減圧下クーゲルロール蒸留により精製することで、４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニル－１，３－ヘキサンジオンの無色油状物を得た（収量５．９ｇ，収率６２％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：１５．３（ｂｒｓ，１Ｈ），７．９７（ｂｒｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．６４（ｔｔ，Ｊ＝７．４，１．３Ｈｚ，１Ｈ），７．５２（ｂｒｄｄ，Ｊ＝８．２，７．４Ｈｚ，２Ｈ），６．６２（ｂｒｓ，１Ｈ）．^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．５（ｔ，Ｊ＝９．５Ｈｚ，３Ｆ），－１２６．１（ｍ，２Ｆ），－１２６．８（ｂｒｓ，２Ｆ）。 (Reference Example 6)

Acetophenone (3.5 mL, 30.0 mmol) was dissolved in ethanol (16.6 mL), and 10 wt% sodium ethoxide in ethanol solution (13.4 mL, 36 mmol) and ethyl heptafluorobutyrate (5.2 mL, 30.0 mmol) were added, followed by stirring for 21 hours under heating and reflux. The reaction mixture was cooled to 0°C, acidified with 10% sulfuric acid, and the aqueous layer was extracted three times with diethyl ether. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by Kugelrohr distillation under reduced pressure to obtain 4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedione as a colorless oil (yield 5.9 g, 62%). ^1H -NMR (400MHz, _CDCl3 ) δ (ppm): 15.3 (brs, 1H), 7.97 (brd, J=8.2Hz, 2H), 7.64 (tt, J=7.4, 1.3Hz, 1H), 7.52 (brdd, J=8.2, 7.4Hz, 2H), 6.62 (brs, 1H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.5 (t, J=9.5 Hz, 3F), -126.1 (m, 2F), -126.8 (brs, 2F).

水素化ナトリウム（流動パラフィン分散物，水素化ナトリウムとして５５％以上含有，１．７９ｇ，４１．０ｍｍｏｌ）をテトラヒドロフラン（１４０ｍＬ）に懸濁し、０℃に冷却した。この懸濁液に２－アセチルチオフェン（４．３ｍＬ，３９．９ｍｍｏｌ）と２－チオフェンカルボン酸エチル（５．４ｍＬ，４０．０ｍｍｏｌ）を加え、室温に昇温させながら１９時間撹拌した。反応混合物に１Ｍ塩酸（５０ｍＬ）を入れ、有機層を分離後、水層をジエチルエーテル（５０ｍＬｘ２）で抽出した。有機層を併せ、水（５０ｍＬ）と飽和食塩水（５０ｍＬ）で洗浄し、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物をヘキサンで洗浄後、減圧下５０℃にて１時間加熱乾燥することで、１，３－ジ（２－チエニル）－１，３－プロパンジオンの黄褐色固体を得た（収量７．２３ｇ，収率７７％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：１６．２（ｂｒｓ，１Ｈ），７．７８（ｄｄ，Ｊ＝３．８，１．２Ｈｚ，２Ｈ），７．６２（ｄｄ，Ｊ＝５．０，１．２Ｈｚ，２Ｈ），７．１７（ｄｄ，Ｊ＝５．０，３．８Ｈｚ，２Ｈ），６．５４（ｂｒｓ，１Ｈ）。 (Reference Example 7)

Sodium hydride (liquid paraffin dispersion, sodium hydride content of 55% or more, 1.79 g, 41.0 mmol) was suspended in tetrahydrofuran (140 mL) and cooled to 0° C. 2-acetylthiophene (4.3 mL, 39.9 mmol) and ethyl 2-thiophenecarboxylate (5.4 mL, 40.0 mmol) were added to this suspension, and the mixture was stirred for 19 hours while warming to room temperature. 1M hydrochloric acid (50 mL) was added to the reaction mixture, the organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL×2). The organic layers were combined, washed with water (50 mL) and saturated saline (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was washed with hexane and dried by heating at 50° C. under reduced pressure for 1 hour to obtain a yellowish brown solid of 1,3-di(2-thienyl)-1,3-propanedione (yield 7.23 g, 77%). ¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 16.2 (brs, 1H), 7.78 (dd, J = 3.8, 1.2Hz, 2H), 7.62 (dd, J = 5.0, 1.2Hz, 2H), 7.17 (dd, J = 5.0, 3.8Hz, 2H) , 6.54 (brs, 1H).

水素化ナトリウム（流動パラフィン分散物，水素化ナトリウムとして５５％以上含有，７１３ｍｇ，１６．３ｍｍｏｌ）をテトラヒドロフラン（５５ｍＬ）に懸濁し、０℃に冷却した。この懸濁液に２－アセトフェノン（１．８ｍＬ，１５．４ｍｍｏｌ）と２－チオフェンカルボン酸エチル（２．１ｍＬ，１５．６ｍｍｏｌ）を加え、室温に昇温して１８時間撹拌した。反応混合物を０℃に冷却し、１Ｍ塩酸（２０ｍＬ）を入れ、有機層を分離した。水層をジエチルエーテル（３０ｍＬｘ２）で抽出し、有機層を併せ、水（２０ｍＬ）と飽和食塩水（２０ｍＬ）で洗浄し、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：ヘキサン／酢酸エチル）にて精製することで、１－フェニル－３－（２－チエニル）－１，３－プロパンジオンの薄黄色固体を得た（収量２．４７ｇ，収率７０％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：１６．３（ｂｒｓ，１Ｈ），７．９５（ｄｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．８２（ｄｄ，Ｊ＝３．８，１．２Ｈｚ，１Ｈ），７．６５（ｄｄ，Ｊ＝４．９，１．１Ｈｚ，１Ｈ），７．５５（ｂｒｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．４９（ｂｒｔ，Ｊ＝８．２，７．５Ｈｚ，２Ｈ），７．１８（ｄｄ，Ｊ＝４．９，３．８Ｈｚ，１Ｈ），６．６９（ｂｒｓ，１Ｈ）。 (Reference Example 8)

Sodium hydride (liquid paraffin dispersion, sodium hydride content of 55% or more, 713 mg, 16.3 mmol) was suspended in tetrahydrofuran (55 mL) and cooled to 0°C. 2-Acetophenone (1.8 mL, 15.4 mmol) and ethyl 2-thiophenecarboxylate (2.1 mL, 15.6 mmol) were added to this suspension, and the mixture was warmed to room temperature and stirred for 18 hours. The reaction mixture was cooled to 0°C, 1M hydrochloric acid (20 mL) was added, and the organic layer was separated. The aqueous layer was extracted with diethyl ether (30 mL x 2), and the organic layers were combined, washed with water (20 mL) and saturated saline (20 mL), 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 pale yellow solid of 1-phenyl-3-(2-thienyl)-1,3-propanedione (yield 2.47 g, 70%). ¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm): 16.3 (brs, 1H), 7.95 (dd, J = 8.2Hz, 2H), 7.82 (dd, J = 3.8, 1.2Hz, 1H), 7.65 (dd, J = 4.9, 1.1Hz, 1H), 7 .55 (brt, J=7.5Hz, 1H), 7.49 (brt, J=8.2, 7.5Hz, 2H), 7.18 (dd, J=4.9, 3.8Hz, 1H), 6.69 (brs, 1H).

水素化ナトリウム（流動パラフィン分散物，水素化ナトリウムとして５５％以上含有，１．７６ｇ，４０．３ｍｍｏｌ）をテトラヒドロフラン（１３５ｍＬ）に懸濁し、０℃に冷却した。この懸濁液に３－アセチルチオフェン（５．０５ｇ，４０．０ｍｍｏｌ）と２－チオフェンカルボン酸エチル（５．４ｍＬ，４０．０ｍｍｏｌ）を加え、室温に昇温して１４時間撹拌した。反応混合物を０℃に冷却し、１Ｍ塩酸（４５ｍＬ）を入れ、有機層を分離後、水層をジエチルエーテル（５０ｍＬｘ２）で抽出した。有機層を併せ、０．５Ｍ塩酸（５０ｍＬ）と飽和食塩水（５０ｍＬ）で洗浄し、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：ヘキサン／酢酸エチル）にて精製し、精製物をヘキサンで洗浄することで、１－（２－チエニル）－３－（３－チエニル）－１，３－プロパンジオンの黄白色固体を得た（収量５．０３ｇ，収率５３％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：１６．１（ｂｒｓ，１Ｈ），７．７８（ｄｄ，Ｊ＝３．８，１．２Ｈｚ，２Ｈ），７．６２（ｄｄ，Ｊ＝５．０，１．２Ｈｚ，２Ｈ），７．１７（ｄｄ，Ｊ＝５．０，３．８Ｈｚ，２Ｈ），６．５４（ｂｒｓ，１Ｈ）。 (Reference Example 9)

Sodium hydride (liquid paraffin dispersion, sodium hydride content of 55% or more, 1.76 g, 40.3 mmol) was suspended in tetrahydrofuran (135 mL) and cooled to 0°C. 3-acetylthiophene (5.05 g, 40.0 mmol) and ethyl 2-thiophenecarboxylate (5.4 mL, 40.0 mmol) were added to this suspension, and the mixture was warmed to room temperature and stirred for 14 hours. The reaction mixture was cooled to 0°C, 1 M hydrochloric acid (45 mL) was added, the organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL x 2). The organic layers were combined, washed with 0.5 M hydrochloric acid (50 mL) and saturated saline (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) and the purified product was washed with hexane to obtain a yellow-white solid of 1-(2-thienyl)-3-(3-thienyl)-1,3-propanedione (yield: 5.03 g, 53%). ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 16.1 (brs, 1H), 7.78 (dd, J = 3.8, 1.2 Hz, 2H), 7.62 (dd, J = 5.0, 1.2 Hz, 2H), 7.17 (dd, J = 5.0, 3.8 Hz, 2H), 6.54 (brs, 1H).

水素化ナトリウム（流動パラフィン分散物，水素化ナトリウムとして５５％以上含有，２．２４ｇ，５１．３ｍｍｏｌ）をテトラヒドロフラン（１７０ｍＬ）に懸濁し、０℃に冷却した。この懸濁液に３－アセチルチオフェン（６．３１ｇ，５０．０ｍｍｏｌ）とトリフルオロ酢酸２，２，２－トリフルオロエチル（６．８ｍＬ，５１．０ｍｍｏｌ）を加え、室温に昇温しながら１２時間撹拌した。反応混合物を０℃に冷却し、１Ｍ塩酸（６０ｍＬ）を入れ、有機層を分離後、水層をジエチルエーテル（５０ｍＬｘ２）で抽出した。有機層を併せ、水（５０ｍＬ）と飽和食塩水（５０ｍＬ）で洗浄し、硫酸ナトリウムで乾燥後、減圧濃縮した。得られた粗生成物を減圧下クーゲルロール蒸留し、続いて―７８℃下ヘキサン／クロロホルムで再結晶して精製することで、４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオンの黄色固体を得た（収量４．２１ｇ，収率３８％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：１４．９０（ｂｒｓ，１Ｈ），８．１９（ｄｄ，Ｊ＝３．０，１．３Ｈｚ，１Ｈ），７．５２（ｄｄ，Ｊ＝５．１，１．３Ｈｚ，１Ｈ），７．４３（ｄｄ，Ｊ＝５．１，３．０Ｈｚ，１Ｈ），６．３９（ｂｒｓ，１Ｈ）．^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７６．４（ｓ）。 (Reference Example 10)

Sodium hydride (liquid paraffin dispersion, sodium hydride content of 55% or more, 2.24 g, 51.3 mmol) was suspended in tetrahydrofuran (170 mL) and cooled to 0°C. 3-acetylthiophene (6.31 g, 50.0 mmol) and 2,2,2-trifluoroethyl trifluoroacetate (6.8 mL, 51.0 mmol) were added to this suspension, and the mixture was stirred for 12 hours while warming to room temperature. The reaction mixture was cooled to 0°C, 1M hydrochloric acid (60 mL) was added, the organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL x 2). The organic layers were combined, washed with water (50 mL) and saturated saline (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by Kugelrohr distillation under reduced pressure, followed by recrystallization from hexane/chloroform at -78°C to give 4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedione as a yellow solid (yield 4.21 g, 38%). ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 14.90 (brs, 1H), 8.19 (dd, J = 3.0, 1.3 Hz, 1H), 7.52 (dd, J = 5.1, 1.3 Hz, 1H), 7.43 (dd, J = 5.1, 3.0 Hz, 1H), 6.39 (brs, 1H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -76.4 (s).

１，３－ジフェニル－１，３－ブタンジオン（３．６８ｇ，１６．４ｍｍｏｌ）にエタノール（４１ｍＬ）と塩化ユウロピウム六水和物（２．００ｇ，５．４６ｍｍｏｌ）の水溶液（５４ｍＬ）を加えた。反応混合物に１Ｍの水酸化ナトリウム水溶液（１６．０ｍＬ，１６．０ｍｍｏｌ）を加え、室温で１時間撹拌した。生じた固体をろ取し、水とエタノールで洗浄し、減圧下５０℃で加熱乾燥した。得られた粗生成物にアセトンを入れ、不溶物をろ過にて除去し、ろ液を濃縮することで、ジアクアトリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）の黄色固体を得た（収量２．７６ｇ，収率５９％）。ＥＳＩＭＳ（ｍ／ｚ）：６３４．０［Ｍ－（１，３－ジフェニル－１，３－ブタンジオナト）］^＋。 (Reference Example 11)

Ethanol (41 mL) and an aqueous solution (54 mL) of europium chloride hexahydrate (2.00 g, 5.46 mmol) were added to 1,3-diphenyl-1,3-butanedione (3.68 g, 16.4 mmol). 1M aqueous sodium hydroxide solution (16.0 mL, 16.0 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The resulting solid was collected by filtration, washed with water and ethanol, and dried by heating at 50° C. under reduced pressure. Acetone was added to the obtained crude product, insoluble matter was removed by filtration, and the filtrate was concentrated to obtain a yellow solid of diaquatris(1,3-diphenyl-1,3-butanedionato)europium(III) (yield 2.76 g, 59%). ESIMS (m/z): 634.0 [M-(1,3-diphenyl-1,3-butanedionato)] ⁺ .

２－ビフェニル（ジシクロヘキシル）ホスフィン（５．１９ｇ，１４．８ｍｍｏｌ）をジクロロメタン（７０ｍＬ）に溶解し、０℃で３０％過酸化水素水（４．４ｍＬ）を加え、室温で５時間撹拌した。反応混合物に水（７０ｍＬ）を入れ、有機層を分離後、水層にクロロホルム（７０ｍＬ）を加え、クロロホルム層を分離した。この操作を２回繰り返した。有機層を併せ、硫酸マグネシウムで乾燥後、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：クロロホルム／メタノール）により精製することで、２－ビフェニル（ジシクロヘキシル）ホスフィンオキシドを白色固体として得た（５．９６ｇ，収率＞９９％）。^１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：８．１１（ｍ，１Ｈ），７．５３～７．４６（ｍ，２Ｈ），７．４５～７．３３（ｍ，３Ｈ），７．２５～７．１９（ｍ，３Ｈ），１．８８～１．７８（ｍ，２Ｈ），１．７８～１．４６（ｍ，８Ｈ），１．４５～０．９６（ｍ，１２Ｈ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：４８．３（ｓ）。 (Reference Example 12)

2-Biphenyl(dicyclohexyl)phosphine (5.19 g, 14.8 mmol) was dissolved in dichloromethane (70 mL), 30% hydrogen peroxide solution (4.4 mL) was added at 0° C., and the mixture was stirred at room temperature for 5 hours. Water (70 mL) was added to the reaction mixture, and the organic layer was separated. Chloroform (70 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 obtained crude product was purified by silica gel column chromatography (eluent: chloroform/methanol) to obtain 2-biphenyl(dicyclohexyl)phosphine oxide as a white solid (5.96 g, yield >99%). ^1H -NMR (400MHz, CDCl ₃ ), δ (ppm): 8.11 (m, 1H), 7.53-7.46 (m, 2H), 7.45-7.33 (m, 3H), 7.25-7.19 (m, 3H), 1.88-1.78 (m, 2H), 1.78-1.46 (m, 8H) ), 1.45-0.96 (m, 12H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 48.3 (s).

酢酸ユウロピウムｎ水和物（２．５水和物として５．６２ｇ，１５ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（８．８９ｇ，３０ｍｍｏｌ）にメタノール（１５０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオン（１０．０ｇ，４５ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で１３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、アセトン／水で再沈殿した。析出した粉末を、アセトン、水で洗浄することでビス（トリシクロヘキシルホスフィンオキシド）トリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－１）の白色固体を得た（収量１８．６ｇ，収率８８％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７９．１（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－５９．２（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１１８５．７［Ｍ－（４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト）］^＋。発光量子収率：８４％（３８０ｎｍ励起）。熱分解温度：３５４℃。 Example 1

Methanol (150 mL) was added to europium acetate n-hydrate (5.62 g, 15 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (8.89 g, 30 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (10.0 g, 45 mmol) was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 13 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then reprecipitated with acetone/water. The precipitated powder was washed with acetone and water to obtain a white solid of bis(tricyclohexylphosphine oxide)tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1-1) (yield 18.6 g, 88%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −79.1 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −59.2 (brs). ESIMS (m/z): 1185.7 [M-(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato)] ⁺ . Emission quantum yield: 84% (380 nm excitation). Thermal decomposition temperature: 354° C.

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．７８ｇ，６．０ｍｍｏｌ）にメタノール（１５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオン（１．９４ｇ，９．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ８になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、ジクロロメタン／メタノールで再結晶することでビス（トリシクロヘキシルホスフィンオキシド）トリス（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１－２）の白色固体を得た（収量２．５８ｇ，収率６２％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７８．７（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－５７．９（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１１７３．６［Ｍ－（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）］^＋。発光量子収率：７６％（３８０ｎｍ励起）。熱分解温度：３３８℃。 Example 2

Methanol (15 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.78 g, 6.0 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-phenyl-1,3-butanedione (1.94 g, 9.0 mmol) was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 8, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then recrystallized from dichloromethane/methanol to obtain a white solid of bis(tricyclohexylphosphine oxide)tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)europium(III) (1-2) (yield: 2.58 g, 62%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −78.7 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −57.9 (brs). ESIMS (m/z): 1173.6 [M-(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)] ⁺ . Emission quantum yield: 76% (380 nm excitation). Thermal decomposition temperature: 338° C.

酢酸ユウロピウムｎ水和物（２．５水和物として３７４ｍｇ，１．０ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（５９３ｍｇ，２．０ｍｍｏｌ）にメタノール（５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオン（９６７ｍｇ，３．０ｍｍｏｌ）／メタノール（２ｍＬ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、ヘキサン／メタノールで再結晶した。析出した粉末を、メタノールで洗浄することでビス（トリシクロヘキシルホスフィンオキシド）トリス［４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオナト］ユウロピウム（ＩＩＩ）（１－３）の白色固体を得た（収量７４０ｍｇ，収率４３％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．７（ｂｒｔ，Ｊ＝８．５Ｈｚ，９Ｆ），－１２４．５（ｂｒｑ，Ｊ＝８．５Ｈｚ，６Ｆ），－１２７．５（ｂｒｓ，６Ｆ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－５３．６（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１３８４．９［Ｍ－（４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオナト）］^＋。 Example 3

Methanol (5 mL) was added to europium acetate n-hydrate (374 mg, 1.0 mmol as the 2.5 hydrate) and tricyclohexylphosphine oxide (593 mg, 2.0 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (967 mg, 3.0 mmol)/methanol (2 mL) was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then recrystallized from hexane/methanol. The precipitated powder was washed with methanol to obtain a white solid of bis(tricyclohexylphosphine oxide)tris[4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato]europium(III) (1-3) (yield: 740 mg, 43%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.7 (brt, J = 8.5 Hz, 9F), -124.5 (brq, J = 8.5 Hz, 6F), -127.5 (brs, 6F). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -53.6 (brs). ESIMS (m/z): 1384.9 [M-(4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．７８ｇ，６．０ｍｍｏｌ）にメタノール（３０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例６で得た４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニルヘキサン－１，３－ジオン（２．８４ｇ，９．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で１７時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、メタノールで洗浄することで、ビス（トリシクロヘキシルホスフィンオキシド）トリス（４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニルヘキサン－１，３－ジオナト）ユウロピウム（ＩＩＩ）（１－４）の白色固体を得た（収量１．４２ｇ，収率２８％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．６（ｂｒｔ，Ｊ＝８．２Ｈｚ，９Ｆ），－１２４．３（ｂｒｓ，６Ｆ），－１２７．６（ｂｒｓ，６Ｆ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－４９．１（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１３７３．６［Ｍ－（４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニルヘキサン－１，３－ジオナト）］^＋。 Example 4

Methanol (30 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.78 g, 6.0 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-dione (2.84 g, 9.0 mmol) obtained in Reference Example 6 was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 17 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then washed with methanol to obtain a white solid of bis(tricyclohexylphosphine oxide)tris(4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-dionato)europium(III) (1-4) (yield 1.42 g, 28%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −80.6 (brt, J=8.2 Hz, 9F), −124.3 (brs, 6F), −127.6 (brs, 6F). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −49.1 (brs). ESIMS (m/z): 1373.6 [M-(4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-dionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．０６ｇ，２．８ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．６７ｇ，５．６ｍｍｏｌ）にメタノール（１４ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例７で得た３－ジ（２－チエニル）－１，３－プロパンジオン（２．０ｇ，８．５ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、メタノールで洗浄することで、ビス（トリシクロヘキシルホスフィンオキシド）トリス［１，３－ジ（２－チエニル）－１，３－プロパンジオナト］ユウロピウム（ＩＩＩ）（１－５）の黄色固体を得た（収量２．５２ｇ，収率６２％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－３３．０（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２１３．１［Ｍ－（１，３－ジ（２－チエニル）－１，３－プロパンジオナト）］^＋。 Example 5

Methanol (14 mL) was added to europium acetate n-hydrate (1.06 g, 2.8 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.67 g, 5.6 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 3-di(2-thienyl)-1,3-propanedione (2.0 g, 8.5 mmol) obtained in Reference Example 7 was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then washed with methanol to obtain a yellow solid of bis(tricyclohexylphosphine oxide)tris[1,3-di(2-thienyl)-1,3-propanedionato]europium(III) (1-5) (yield 2.52 g, 62%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −33.0 (brs). ESIMS (m/z): 1213.1 [M-(1,3-di(2-thienyl)-1,3-propanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．７８ｇ，６．０ｍｍｏｌ）にメタノール（２０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に１，３－ジフェニル－１，３－プロパンジオン（２．０２ｇ，９．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、ジクロロメタンで抽出した。濃縮後、メタノールで洗浄することでビス（トリシクロヘキシルホスフィンオキシド）トリス（１，３－ジフェニル－１，３－プロパンジオナト）ユウロピウム（ＩＩＩ）（１－６）の白色固体を得た（収量７６４ｍｇ，収率１８％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－２４．９（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１１８９．７［Ｍ－（１，３－ジフェニル－１，３－プロパンジオナト）］^＋。 (Example 6)

Methanol (20 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.78 g, 6.0 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 1,3-diphenyl-1,3-propanedione (2.02 g, 9.0 mmol) was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then extracted with dichloromethane. After concentration, the mixture was washed with methanol to obtain a white solid of bis(tricyclohexylphosphine oxide)tris(1,3-diphenyl-1,3-propandionato)europium(III) (1-6) (yield: 764 mg, 18%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −24.9 (brs). ESIMS (m/z): 1189.7 [M-(1,3-diphenyl-1,3-propanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．２０ｇ，３．２ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．８８ｇ，６．４ｍｍｏｌ）にメタノール（１６ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例８で得た１－フェニル－３－（２－チエニル）－１，３－プロパンジオン（２．２１ｇ，９．６ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、ジクロロメタン／メタノールで再結晶することでビス（トリシクロヘキシルホスフィンオキシド）トリス［１－フェニル－３－（２－チエニル）－１，３－プロパンジオナト］ユウロピウム（ＩＩＩ）（１－７）の黄色固体を得た（収量１．５２ｇ，収率３３％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－４２．３（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２０２．３［Ｍ－（１－フェニル－３－（２－チエニル）－１，３－プロパンジオナト）］^＋。 (Example 7)

Methanol (16 mL) was added to europium acetate n-hydrate (1.20 g, 3.2 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.88 g, 6.4 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 1-phenyl-3-(2-thienyl)-1,3-propanedione (2.21 g, 9.6 mmol) obtained in Reference Example 8 was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then recrystallized from dichloromethane/methanol to obtain a yellow solid of bis(tricyclohexylphosphine oxide)tris[1-phenyl-3-(2-thienyl)-1,3-propanedionato]europium(III) (1-7) (yield: 1.52 g, 33%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −42.3 (brs). ESIMS (m/z): 1202.3 [M-(1-phenyl-3-(2-thienyl)-1,3-propanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として３．７４ｇ，１０．０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（６．４０ｇ，２０．０ｍｍｏｌ）にメタノール（５０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオン（６．６６ｇ，３０．０ｍｍｏｌ）を加えて室温で３時間撹拌した。反応液を水中にあけ、析出した固体を吸引濾取後水洗した。この固体をシクロペンチルメチルエーテルに溶解し、５０％（ｖ／ｖ）メタノール水溶液で洗浄した後にシクロペンチルメチルエーテル層を減圧濃縮することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－８）の淡黄色固体を得た（収量４．４６ｇ，収率３１％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．６（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８３．８（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２３５．３［Ｍ－（４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト）］^＋。発光量子収率：５２％（３８０ｎｍ励起）。 (Example 8)

Methanol (50 mL) was added to europium acetate n-hydrate (3.74 g, 10.0 mmol as the 2.5 hydrate) and tri(o-tolyl)phosphine oxide (6.40 g, 20.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (6.66 g, 30.0 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water, and the precipitated solid was collected by suction filtration and then washed with water. This solid was dissolved in cyclopentyl methyl ether, washed with 50% (v/v) aqueous methanol solution, and the cyclopentyl methyl ether layer was concentrated under reduced pressure to obtain a pale yellow solid of bis[tri(o-tolyl)phosphine oxide]tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1-8) (yield: 4.46 g, 31%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.6 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -83.8 (brs). ESIMS (m/z): 1235.3 [M-(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato)] ⁺ . Emission quantum yield: 52% (380 nm excitation).

ジアクアトリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（２１４ｍｇ，０．２５１ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（１６３ｍｇ，０．５０９ｍｍｏｌ）にアセトン（５０ｍＬ）を加え、加熱還流下で１５時間撹拌した。反応混合物を室温に放冷後、反応液を減圧濃縮し、ヘキサン／クロロホルムで洗浄することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－８）の白色固体を得た（収量３１３ｍｇ，収率８６％）。 (Example 9)

Acetone (50 mL) was added to diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (214 mg, 0.251 mmol) and tri(o-tolyl)phosphine oxide (163 mg, 0.509 mmol) obtained in Reference Example 4, and the mixture was stirred for 15 hours under heating and reflux. The reaction mixture was allowed to cool to room temperature, and then the reaction solution was concentrated under reduced pressure and washed with hexane/chloroform to obtain a white solid of bis[tri(o-tolyl)phosphine oxide]tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1-8) (yield 313 mg, 86%).

酢酸ユウロピウムｎ水和物（２．５水和物として３．７４ｇ，１０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（６．４０ｇ，２０ｍｍｏｌ）にメタノール（５０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオン（６．４８ｇ，３０ｍｍｏｌ）を加えて室温で３時間撹拌した。反応液を水中にあけ、析出した固体をろ取後水洗した。この固体をヘキサンに溶解し、６０％（ｖ／ｖ）メタノール水溶液で洗浄した後にヘキサン層を減圧濃縮することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１－９）の淡黄色固体を得た（収量１０．６ｇ，収率７４％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．２（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８７．７（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２２３．１［Ｍ－（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）］^＋。発光量子収率：４９％（３８０ｎｍ励起）。 (Example 10)

Methanol (50 mL) was added to europium acetate n-hydrate (3.74 g, 10 mmol as 2.5 hydrate) and tri(o-tolyl)phosphine oxide (6.40 g, 20 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-phenyl-1,3-butanedione (6.48 g, 30 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water, and the precipitated solid was collected by filtration and washed with water. This solid was dissolved in hexane, washed with a 60% (v/v) aqueous methanol solution, and the hexane layer was concentrated under reduced pressure to obtain a pale yellow solid of bis[tri(o-tolyl)phosphine oxide]tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)europium(III) (1-9) (yield: 10.6 g, 74%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −80.2 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −87.7 (brs). ESIMS (m/z): 1223.1 [M-(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)] ⁺ . Emission quantum yield: 49% (380 nm excitation).

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（１．９２ｇ，６．０ｍｍｏｌ）にメタノール（５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオン（２．９０ｇ，９．０ｍｍｏｌ）／メタノール（２ｍＬ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で１３時間撹拌した。反応液を減圧濃縮し、水、メタノール／水混合溶媒で洗浄することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス［４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオナト］ユウロピウム（ＩＩＩ）（１－１０）の白色固体を得た（収量３．２８ｇ，収率６２％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．９（ｂｒｔ，Ｊ＝８．０Ｈｚ，９Ｆ），－１２５．４（ｂｒｓ，６Ｆ），－１２８．１（ｂｒｓ，６Ｆ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－９５．５．ＥＳＩＭＳ（ｍ／ｚ）：１４３２．９［Ｍ－（４，４，５，５，６，６，６－ヘプタフルオロ－１－（２－チエニル）－１，３－ヘキサンジオナト）］^＋。 (Example 11)

Methanol (5 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as the 2.5 hydrate) and tri(o-tolyl)phosphine oxide (1.92 g, 6.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (2.90 g, 9.0 mmol)/methanol (2 mL) was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 13 hours. The reaction solution was concentrated under reduced pressure and washed with water and a mixed solvent of methanol and water to obtain a white solid of bis[tri(o-tolyl)phosphine oxide]tris[4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato]europium(III) (1-10) (yield: 3.28 g, 62%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.9 (brt, J = 8.0 Hz, 9F), -125.4 (brs, 6F), -128.1 (brs, 6F). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -95.5. ESIMS (m/z): 1432.9 [M-(4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（１．９２ｇ，６．０ｍｍｏｌ）にメタノール（１５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例６で得た４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニル－１，３－ヘキサンジオン（２．８５ｇ，９．０ｍｍｏｌ）を加えて室温で３時間撹拌した。反応液を水中にあけ、析出した固体を吸引濾取後水洗した。この固体をヘキサンに溶解し、６０％（ｖ／ｖ）メタノール水溶液で洗浄した後にヘキサン層を減圧濃縮することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス（４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニル－１，３－ヘキサンジオナト）ユウロピウム（ＩＩＩ）（１－１１）の淡黄色固体を得た（収量２．９９ｇ，収率５７％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．９（ｔ，Ｊ＝８．４Ｈｚ），－１２５．１（ｂｒｓ），－１２８．２（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－９４．７（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１４２３．４［Ｍ－（４，４，５，５，６，６，６－ヘプタフルオロ－１－フェニル－１，３－ヘキサンジオナト）］^＋。 Example 12

Methanol (15 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as the 2.5 hydrate) and tri(o-tolyl)phosphine oxide (1.92 g, 6.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedione (2.85 g, 9.0 mmol) obtained in Reference Example 6 was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water, and the precipitated solid was collected by suction filtration and then washed with water. This solid was dissolved in hexane, washed with 60% (v/v) aqueous methanol solution, and the hexane layer was concentrated under reduced pressure to obtain a pale yellow solid of bis[tri(o-tolyl)phosphine oxide]tris(4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedionato)europium(III) (1-11) (yield: 2.99 g, 57%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.9 (t, J = 8.4 Hz), -125.1 (brs), -128.2 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -94.7 (brs). ESIMS (m/z): 1423.4 [M-(4,4,5,5,6,6,6-heptafluoro-1-phenyl-1,3-hexanedionato)] ⁺ .

参考例１１で得たジアクアトリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１．４１ｇ，１．６５ｍｍｏｌ）にアセトン（２２０ｍＬ）に溶解し、参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（１．８９ｇ，５．９０ｍｍｏｌ）を加えて、室温で４時間撹拌した。反応液を減圧濃縮し、ヘキサン／アセトンで再沈殿することで、ビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１－１３）の黄白色固体を得た（収量２．２７ｇ，収率９４％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７６．６（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１２３７．９［Ｍ－（１，３－ジフェニル－１，３－ブタンジオナト）］^＋。発光量子収率：５７％（３８０ｎｍ励起）。熱分解温度：３９６℃。 Example 13

Diaquatris(1,3-diphenyl-1,3-butanedionato)europium(III) (1.41 g, 1.65 mmol) obtained in Reference Example 11 was dissolved in acetone (220 mL), and tri(o-tolyl)phosphine oxide (1.89 g, 5.90 mmol) obtained in Reference Example 4 was added thereto, and the mixture was stirred at room temperature for 4 hours. The reaction solution was concentrated under reduced pressure, and reprecipitated with hexane/acetone to obtain a yellow-white solid of bis[tri(o-tolyl)phosphine oxide]tris(1,3-diphenyl-1,3-butanedionato)europium(III) (1-13) (yield: 2.27 g, 94%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −76.6 (brs). ESIMS (m/z) 1237.9 [M-(1,3-diphenyl-1,3-butanedionato)] ⁺ . Emission quantum yield: 57% (380 nm excitation). Thermal decomposition temperature: 396°C.

酢酸ユウロピウムｎ水和物（２．５水和物として３７４ｍｇ，１．０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（６４０ｍｇ，２．０ｍｍｏｌ）にメタノール（５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に１，３－ジフェニル－１，３－プロパンジオン（６７３ｍｇ，３．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で１３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、メタノールで抽出した。濃縮後、メタノール／ヘキサンで再沈殿することで、ビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス（１，３－ジフェニル－１，３－プロパンジオナト）ユウロピウム（ＩＩＩ）（１－１３）の紅白色固体を得た（収量７４０ｍｇ，収率５１％）。 (Example 14)

Methanol (5 mL) was added to europium acetate n-hydrate (374 mg, 1.0 mmol as hemipentahydrate) and tri(o-tolyl)phosphine oxide (640 mg, 2.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 1,3-diphenyl-1,3-propanedione (673 mg, 3.0 mmol) was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 13 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then extracted with methanol. After concentration, the mixture was reprecipitated with methanol/hexane to obtain a red-white solid of bis[tri(o-tolyl)phosphine oxide]tris(1,3-diphenyl-1,3-propandionato)europium(III) (1-13) (yield: 740 mg, 51%).

参考例１で得たジアクアトリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（８５１ｍｇ，１．００ｍｍｏｌ）と参考例５で得た２－（ジフェニルホスフィノオキシド）ビフェニル（７０９ｍｇ，２．００ｍｍｏｌ）にアセトン（１００ｍＬ）を加え、室温で３．５時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、メタノールとアセトンでそれぞれ再結晶することで、ビス［２－（ジフェニルホスフィノオキシド）ビフェニル］トリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－１５）の白橙色固体を得た（収量１．２３ｇ，収率８１％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７９．９（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７８．７（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１３０３．７［Ｍ－（４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト）］^＋。 (Example 15)

Acetone (100 mL) was added to diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (851 mg, 1.00 mmol) obtained in Reference Example 1 and 2-(diphenylphosphino oxide)biphenyl (709 mg, 2.00 mmol) obtained in Reference Example 5, and the mixture was stirred at room temperature for 3.5 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure and recrystallized from methanol and acetone, respectively, to obtain a whitish orange solid of bis[2-(diphenylphosphino oxide)biphenyl]tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1-15) (yield 1.23 g, 81%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −79.9 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −78.7 (brs). ESIMS (m/z) 1303.7 [M-(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato)] ⁺ .

参考例２で得たジアクアトリス（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（８３３ｍｇ，１．００ｍｍｏｌ）と参考例５で得た２－（ジフェニルホスフィノオキシド）ビフェニル（７０９ｍｇ，２．００ｍｍｏｌ）にアセトン（１００ｍＬ）を加え、室温で３．５時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、メタノールで再結晶することで、ビス［２－（ジフェニルホスフィノオキシド）ビフェニル］トリス［４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－１６）の紅白色固体を得た（収量１．２９ｇ，収率８６％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７９．８（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７５．９（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１２９１．６［Ｍ－（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）］^＋。 (Example 16)

Acetone (100 mL) was added to diaquatris(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)europium(III) (833 mg, 1.00 mmol) obtained in Reference Example 2 and 2-(diphenylphosphino oxide)biphenyl (709 mg, 2.00 mmol) obtained in Reference Example 5, and the mixture was stirred at room temperature for 3.5 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure and recrystallized from methanol to obtain a red-white solid of bis[2-(diphenylphosphino oxide)biphenyl]tris[4,4,4-trifluoro-1-phenyl-1,3-butanedionato]europium(III) (1-16) (yield: 1.29 g, 86%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ(ppm): -79.8 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −75.9 (brs). ESIMS (m/z) 1291.6 [M-(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)] ⁺ .

参考例１１で得たジアクアトリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（８５８ｍｇ，１．００ｍｍｏｌ）と参考例５で得た２－（ビフェニル）ジフェニルホスフィンオキシド（７０９ｍｇ，２．００ｍｍｏｌ）にアセトン（１００ｍＬ）を加え、室温で１７．５時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、ヘキサン／アセトンで再沈殿し、残渣をヘキサンで洗浄して減圧乾燥することで、ビス［２－（ビフェニル）ジフェニルホスフィンオキシド］トリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１－２０）の黄白色固体を得た（収量１．２４ｇ，収率８１％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－４８．３（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１３０５．３［Ｍ－（１，３－ジフェニル－１，３－ブタンジオナト）］^＋。 (Example 17)

Acetone (100 mL) was added to diaquatris(1,3-diphenyl-1,3-butanedionato)europium(III) (858 mg, 1.00 mmol) obtained in Reference Example 11 and 2-(biphenyl)diphenylphosphine oxide (709 mg, 2.00 mmol) obtained in Reference Example 5, and the mixture was stirred at room temperature for 17.5 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure, reprecipitated with hexane/acetone, and the residue was washed with hexane and dried under reduced pressure to obtain a yellowish white solid of bis[2-(biphenyl)diphenylphosphine oxide]tris(1,3-diphenyl-1,3-butanedionato)europium(III) (1-20) (yield: 1.24 g, 81%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -48.3 (brs). ESIMS (m/z) 1305.3 [M-(1,3-diphenyl-1,3-butanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例３で得たトリシクロヘキシルホスフィンオキシド（１．７８ｇ，６．０ｍｍｏｌ）にメタノール（３０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例１０で得た４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオン（２．００ｇ，９．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で１８時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、メタノールで洗浄し、ヘキサン／アセトンから再結晶にて精製することで、ビス（トリシクロヘキシルホスフィンオキシド）トリス［４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－２２）の白色固体を得た（収量９２３ｍｇ，収率２２％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－７９．０（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－５８．８（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１１８７．８［Ｍ－（４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオナト）］^＋。 (Example 18)

Methanol (30 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (1.78 g, 6.0 mmol) obtained in Reference Example 3, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedione (2.00 g, 9.0 mmol) obtained in Reference Example 10 was added to the reaction mixture. A few drops of ammonia water were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 18 hours. The reaction solution was concentrated under reduced pressure, washed with water, washed with methanol, and purified by recrystallization from hexane/acetone to obtain a white solid of bis(tricyclohexylphosphine oxide)tris[4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedionato]europium(III) (1-22) (yield 923 mg, 22%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −79.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −58.8 (brs). ESIMS (m/z): 1187.8 [M-(4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例４で得たトリ（ｏ－トリル）ホスフィンオキシド（１．９２ｇ，６.０ｍｍｏｌ）にメタノール（１５ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例１０で得た４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオン（２．００ｇ，９．０ｍｍｏｌ）を加えて室温で３時間撹拌した。反応液を水中にあけ、析出した固体を吸引ろ取後水洗した。この固体をシクロペンチルメチルエーテルに溶解し、５０％（ｖ／ｖ）メタノール水溶液で洗浄した後にシクロペンチルメチルエーテル層を減圧濃縮することでビス［トリ（ｏ－トリル）ホスフィンオキシド］トリス［４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－２３）の淡黄色固体を得た（収量３．５６ｇ，収率８２％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．１（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８７．９（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２３５．７［Ｍ－（４，４，４－トリフルオロ－１－（３－チエニル）－１，３－ブタンジオナト）］^＋。 (Example 19)

Methanol (15 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as the 2.5 hydrate) and tri(o-tolyl)phosphine oxide (1.92 g, 6.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedione (2.00 g, 9.0 mmol) obtained in Reference Example 10 was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water, and the precipitated solid was collected by suction filtration and then washed with water. This solid was dissolved in cyclopentyl methyl ether, washed with 50% (v/v) aqueous methanol solution, and the cyclopentyl methyl ether layer was concentrated under reduced pressure to obtain a pale yellow solid of bis[tri(o-tolyl)phosphine oxide]tris[4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedionato]europium(III) (1-23) (yield: 3.56 g, 82%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): -80.1 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): -87.9 (brs). ESIMS (m/z): 1235.7 [M-(4,4,4-trifluoro-1-(3-thienyl)-1,3-butanedionato)] ⁺ .

参考例１で得たジアクアトリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１．７０ｇ，２．００ｍｍｏｌ）と参考例１２で得た２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド（１．４７ｇ，４．００ｍｍｏｌ）にアセトン（２００ｍＬ）を加え、室温で４時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、ヘキサン／アセトンで再沈殿し、残渣をヘキサンで洗浄して減圧乾燥することで、ビス［２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド］トリス［４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－２５）の橙白色固体を得た（収量２．６９ｇ，収率８７％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．０（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－６６．８（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１３２６．５［Ｍ－（４，４，４－トリフルオロ－１－（２－チエニル）－１，３－ブタンジオナト）］^＋。 (Example 20)

Acetone (200 mL) was added to diaquatris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1.70 g, 2.00 mmol) obtained in Reference Example 1 and 2-biphenyl(dicyclohexyl)phosphine oxide (1.47 g, 4.00 mmol) obtained in Reference Example 12, and the mixture was stirred at room temperature for 4 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure, reprecipitated with hexane/acetone, and the residue was washed with hexane and dried under reduced pressure to obtain an orange-white solid of bis[2-biphenyl(dicyclohexyl)phosphine oxide]tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) (1-25) (yield 2.69 g, 87%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −80.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −66.8 (brs). ESIMS (m/z) 1326.5 [M-(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato)] ⁺ .

参考例２で得たジアクアトリス［４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１．６７ｇ，２．００ｍｍｏｌ）と参考例１２で得た２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド（１．４７ｇ，４．００ｍｍｏｌ）にアセトン（２００ｍＬ）を加え、室温で４時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、ヘキサン／アセトンで再沈殿し、残渣をヘキサンで洗浄して減圧乾燥することで、ビス［２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド］トリス［４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト］ユウロピウム（ＩＩＩ）（１－２６）の白橙色固体を得た（収量２．４３ｇ，収率７９％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－８０．２（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－６４．９（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１３１４．３［Ｍ－（４，４，４－トリフルオロ－１－フェニル－１，３－ブタンジオナト）］^＋。 (Example 21)

Acetone (200 mL) was added to diaquatris[4,4,4-trifluoro-1-phenyl-1,3-butanedionato]europium(III) (1.67 g, 2.00 mmol) obtained in Reference Example 2 and 2-biphenyl(dicyclohexyl)phosphine oxide (1.47 g, 4.00 mmol) obtained in Reference Example 12, and the mixture was stirred at room temperature for 4 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure, reprecipitated with hexane/acetone, and the residue was washed with hexane and dried under reduced pressure to obtain a whitish orange solid of bis[2-biphenyl(dicyclohexyl)phosphine oxide]tris[4,4,4-trifluoro-1-phenyl-1,3-butanedionato]europium(III) (1-26) (yield: 2.43 g, 79%). ¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ (ppm): −80.2 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −64.9 (brs). ESIMS (m/z) 1314.3 [M-(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)] ⁺ .

参考例１１で得たジアクアトリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１．７２ｇ，２．００ｍｍｏｌ）と参考例１２で得た２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド（１．４７ｇ，４．００ｍｍｏｌ）にアセトン（２００ｍＬ）を加え、室温で１７．５時間撹拌した。ろ過により不溶物を除去した後、反応液を減圧濃縮し、ヘキサン／アセトンで再沈殿し、残渣をヘキサンで洗浄して減圧乾燥することで、ビス［２－ビフェニル（ジシクロヘキシル）ホスフィンオキシド］トリス（１，３－ジフェニル－１，３－ブタンジオナト）ユウロピウム（ＩＩＩ）（１－２７）の黄白色固体を得た（収量２．５６ｇ，収率８２％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－３２．８（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）１３２９．８［Ｍ－（１，３－ジフェニル－１，３－ブタンジオナト）］^＋。 (Example 22)

Acetone (200 mL) was added to diaquatris(1,3-diphenyl-1,3-butanedionato)europium(III) (1.72 g, 2.00 mmol) obtained in Reference Example 11 and 2-biphenyl(dicyclohexyl)phosphine oxide (1.47 g, 4.00 mmol) obtained in Reference Example 12, and the mixture was stirred at room temperature for 17.5 hours. After removing insoluble matter by filtration, the reaction solution was concentrated under reduced pressure, reprecipitated with hexane/acetone, and the residue was washed with hexane and dried under reduced pressure to obtain a yellowish white solid of bis[2-biphenyl(dicyclohexyl)phosphine oxide]tris(1,3-diphenyl-1,3-butanedionato)europium(III) (1-27) (yield: 2.56 g, 82%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −32.8 (brs). ESIMS (m/z) 1329.8 [M-(1,3-diphenyl-1,3-butanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（２．５水和物として１．１２ｇ，３．０ｍｍｏｌ）と参考例４で得たトリシクロヘキシルホスフィンオキシド（２．１２ｇ，６．０ｍｍｏｌ）にメタノール（３０ｍＬ）を加え、室温で１時間撹拌した。反応混合物に参考例９で得た１－（２－チエニル）－３－（３－チエニル）－１，３－プロパンジオン（２．１２ｇ，９．０ｍｍｏｌ）を加えた。アンモニア水を反応液がｐＨ７になるまで数滴滴下し、室温で３時間撹拌した。反応液を減圧濃縮し、水で洗浄した後、ヘキサンで洗浄した。得られた粗生成物をヘキサン／アセトンで再結晶し、続いて少量のメタノールで洗浄した。得られた固体にジエチルエーテルを加え、不溶物を吸引ろ過にて除去し、ろ液を濃縮することで、ビス（トリシクロヘキシルホスフィンオキシド）トリス［１－（２－チエニル）－３－（３－チエニル）－１，３－プロパンジオナト］ユウロピウム（ＩＩＩ）（１－２８）の黄色固体を得た（収量５８４ｍｇ，収率１３％）。^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：－３０．２（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１２１３．９［Ｍ－（１－（２－チエニル）－３－（３－チエニル）－１，３－プロパンジオナト）］^＋。 (Example 23)

Methanol (30 mL) was added to europium acetate n-hydrate (1.12 g, 3.0 mmol as 2.5 hydrate) and tricyclohexylphosphine oxide (2.12 g, 6.0 mmol) obtained in Reference Example 4, and the mixture was stirred at room temperature for 1 hour. 1-(2-thienyl)-3-(3-thienyl)-1,3-propanedione (2.12 g, 9.0 mmol) obtained in Reference Example 9 was added to the reaction mixture. A few drops of aqueous ammonia were added until the reaction solution reached pH 7, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, washed with water, and then washed with hexane. The obtained crude product was recrystallized from hexane/acetone, and then washed with a small amount of methanol. Diethyl ether was added to the obtained solid, insoluble matter was removed by suction filtration, and the filtrate was concentrated to obtain a yellow solid of bis(tricyclohexylphosphine oxide)tris[1-(2-thienyl)-3-(3-thienyl)-1,3-propanedionato]europium(III) (1-28) (yield: 584 mg, 13%). ³¹ P-NMR (162 MHz, CDCl ₃ ) δ (ppm): −30.2 (brs). ESIMS (m/z): 1213.9 [M-(1-(2-thienyl)-3-(3-thienyl)-1,3-propanedionato)] ⁺ .

酢酸ユウロピウムｎ水和物（８．０ｇ，２．５水和物として２１ｍｍｏｌ）に純水（１００ｍＬ）を加え、室温で１０分撹拌した。反応混合物にヘキサフルオロアセチルアセトン（１６．７ｇ，８０．２ｍｍｏｌ）を滴下後、５０℃で３時間撹拌した。得られた白色懸濁液をろ別し、得られた白色固体を水（２００ｍＬ）、トルエン（２００ｍＬ）で洗浄することで、ジアクアトリス（ヘキサフルオロアセチルアセトナト）ユウロピウム（ＩＩＩ）を白色固体として得た（収量１１．６ｇ，酢酸ユウロピウム２．５水和物を２１ｍｍｏｌ使用したとして収率６８％）。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，Ａｃｅｔｏｎｅ－ｄ_６），δ（ｐｐｍ）：－８１．２（ｂｒｓ）．ＥＳＩＭＳ（ｍ／Ｚ）：５６６．８［Ｍ－（ヘキサフルオロアセチルアセトナト）］^＋。 (Comparative Example 1)

Pure water (100 mL) was added to europium acetate n-hydrate (8.0 g, 21 mmol as 2.5 hydrate) and stirred at room temperature for 10 minutes. Hexafluoroacetylacetone (16.7 g, 80.2 mmol) was added dropwise to the reaction mixture, and 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 obtain diaquatris(hexafluoroacetylacetonato)europium(III) as a white solid (yield 11.6 g, 68% yield assuming 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-(hexafluoroacetylacetonate)] ⁺ .

アルゴン雰囲気下、比較例１で得たジアクアトリス（ヘキサフルオロアセチルアセトナト）ユウロピウム（ＩＩＩ）（５．０ｇ，６．１８ｍｍｏｌ）とトリフェニルホスフィンオキシド（３．４ｇ，１２．４ｍｍｏｌ）にエタノール（２００ｍＬ）を加え、６５℃で３時間撹拌した。反応液をろ過し、ろ液を減圧濃縮し、メタノールで再結晶することで、ビス（トリフェニルホスフィンオキシド）トリス（ヘキサフルオロアセチルアセトナト）ユウロピウム（ＩＩＩ）の白色固体を得た（収量４．８ｇ，収率５８％）。なお、この化合物は、ＲＵＢ１４５３８６０及び日本特開２００３－８１９８６号公報に具体的に記載されている化合物である。^１９Ｆ－ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：－７９．０（ｂｒｓ）．^３１Ｐ－ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３），δ（ｐｐｍ）：－９１．３（ｂｒｓ）．ＥＳＩＭＳ（ｍ／ｚ）：１１２３．４［Ｍ (Comparative Example 2)

Under an argon atmosphere, ethanol (200 mL) was added to diaquatris(hexafluoroacetylacetonato)europium(III) (5.0 g, 6.18 mmol) obtained in Comparative Example 1 and triphenylphosphine oxide (3.4 g, 12.4 mmol), and the mixture was stirred at 65° C. for 3 hours. The reaction solution was filtered, 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: 4.8 g, 58%). This compound is specifically described in RUB1453860 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

(Evaluation Example)
The sample for measuring excitation and spectrum of the europium complex obtained in the examples was prepared by crushing the europium complex powder in a mortar until it became a fine powder, and filling it into a powder cell (PSH-002, manufactured by JASCO Corporation).
The measurement results of the excitation and emission spectra of the europium complexes obtained in the examples are shown in Figures 1 to 19. The conditions for measuring the excitation spectrum were an emission detection wavelength of 615 nm, an excitation side slit of 5 nm, a fluorescence side slit of 5 nm, and a 420 nm sharp cut filter was used on the detector side. The conditions for measuring the emission spectrum were an excitation light of 380 nm, an excitation side slit of 1 nm, and a fluorescence side slit of 1 nm. Emissions at approximately 593 nm, 615 nm, 653 nm, and 699 nm due to the ff electronic transition characteristic of Eu(III) complexes were observed.

The solubility of the europium complex was evaluated by testing the saturated solubility concentration. An excess amount of europium complex was added to 5 mL of chloroform and stirred at 20° C. for 10 minutes. A certain amount (0.5 mL) of the supernatant of this saturated solution was taken and heated on a hot plate at 85° C. for 60 minutes to evaporate the solvent. Then, it was dried at 60° C. for 60 minutes under reduced pressure. The saturated solubility concentration was calculated from the solution mass before drying and the solute mass after drying, and the results are shown in Table 1.
Saturation solubility concentration (%)=(solute mass after drying)/(solution mass before drying)×100

表１に表したように、本発明のユウロピウム錯体（１）は、高い溶解性を有することがわかった。

As shown in Table 1, the europium complex (1) of the present invention was found to have high solubility.

A sample for measuring the UV-Vis spectrum of the europium complex of the present invention was prepared by dissolving the europium complex obtained in the examples in chloroform for spectroscopic analysis at a predetermined concentration and filling a 1 cm quartz cell for spectroscopic analysis.
The results of measuring the UV-Vis spectrum of the europium complex obtained in the examples are shown in Figures 20 to 24. In each figure, the inset in the upper right corner shows the vicinity of the absorption edge of the UV-Vis spectrum at a given concentration.
20 also shows the results of Comparative Example 2. The complex of Comparative Example 2 is inferior to the europium complex of the present invention in terms of its ability to absorb long-wavelength ultraviolet light.
In other words, the europium complex of the present invention has high absorption ability for long-wavelength ultraviolet light and high solubility.

The europium complex (1) of the present invention is useful as an luminescent material such as a film for a solar cell, an agricultural film, an LED phosphor, an organic electroluminescent material, or a security ink, or as a wavelength conversion material used therein.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2019-099936, filed on May 29, 2019, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (14)

A europium complex represented by any one of the following formulas (1-1) to (1-29):

2. The europium complex according to claim 1 , which is represented by any one of ( 1-1) to (1-11), (1-13), (1-15), (1-16) and (1-20). 3. The europium complex according to claim 1, which is represented by any one of ( 1-1) to (1-4), (1-6), (1-8) to (1-11), (1-13), (1-15), (1-16) and (1-20). 4. The europium complex according to claim 1, which is represented by any one of ( 1-1), (1-2), (1-6), (1-8), (1-9) and (1-13). The europium complex according to any one of claims 1 to 4, which is represented by any one of ( 1-8), (1-9) and (1-13). A method for producing a europium complex (1) represented by the following formula (1) ,

(In the formula, R ¹ , R ² and R ³ each independently represent a cyclic secondary alkyl group having 3 to 10 carbon atoms or a phenyl group represented by the following formula (2); however, R ¹ , R ² and R ³ are not all phenyl groups at the same time, and one of R ¹ , R ² and R ³ is not a cyclohexyl group and two are not phenyl groups. ^{W 1} and W ² each independently represent a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group.)

(In the formula, X1 ^represents a hydrogen 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 phenyl group which 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, or a fluoroalkyl group having 1 to 3 carbon atoms.)
A production method comprising reacting a phosphine oxide represented by the following formula (4), a β-diketone represented by the following formula (3) (hereinafter referred to as 3), with a europium salt.

(In the formula, R ¹ , R ² , R ³ , W ¹ and W ² have the same meanings as R ¹ , R ² , R ³ , W ¹ and W ² in the formula (1).) A method for producing a europium complex (1) represented by the following formula (1) ,

(In the formula, R ¹ , R ² and R ³ each independently represent a cyclic secondary alkyl group having 3 to 10 carbon atoms or a phenyl group represented by the following formula (2); however, R ¹ , R ² and R ³ are not all phenyl groups at the same time, and one of R ¹ , R ² and R ³ is not a cyclohexyl group and two are not phenyl groups. ^{W 1} and W ² each independently represent a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group.)

(In the formula, X1 ^represents a hydrogen 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 phenyl group which 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, or a fluoroalkyl group having 1 to 3 carbon atoms.)
A production method comprising reacting a diketonato complex (5) represented by the following formula (5) with a phosphine oxide (4) represented by the following formula (4):

(In the formula, R ¹ , R ² , R ³ , W ¹ and W ² have the same meanings as R ¹ , R ² , R ³ , W ¹ and W ² in the formula (1), Q represents a coordination molecule, and m represents an integer of 0 to 3.) The method for producing a europium complex (1) according to claim 6 or 7, wherein in said formula (1), R ¹ , R ² and R ³ each independently represent a cyclohexyl group, a 2-biphenyl group or a 2-methylphenyl group . The method for producing the europium complex (1) according to claim 7, wherein Q is water. An optical material comprising the europium complex according to any one of claims 1 to 5 . 11. The optical material according to claim 10, comprising the europium complex according to any one of claims 1 to 5 in a resin material, an inorganic glass, an organic low-molecular-weight material, or a solvent. The optical material according to claim 11, wherein the resin material is polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyethylene, polystyrene, polyvinyl acetate, or a copolymer thereof. The optical material according to claim 11, wherein the solvent is a halogenated hydrocarbon, an alcohol, an ester, a glycol ether, an ether, a ketone, or a hydrocarbon. The optical material according to any one of claims 10 to 13, which is a film for a solar cell, an agricultural film, an LED phosphor, an organic EL material, a light-emitting material, a fluorescent material, or a wavelength conversion material.

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