JP2019094332A - Europium complex and application thereof - Google Patents

Abstract

To provide an Eu complex having high light stability.SOLUTION: There is provided an Eu complex represented by the general formula (1). In the formula, Zto Zare each independently C1 to 3 alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, naphthyl substituted/unsubstituted wit F, pyridyl or a group represented by the general formula (2); -PhRRRRR(2), wherein R, Rand Rare each independently H, F, C1 to 3 alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, phenyl substituted/unsubstituted wit F, a hydroxyl group or a CN group; Rand Rare each independently H or F; Zto Zare not H at same time; Wand Ware each independently C1 to 6 alkyl, fluoroalkyl, phenyl, 2-thienyl or 3-thienyl.SELECTED DRAWING: None

Description

  The present invention relates to a europium complex having high light fastness and an optical material containing the same.

  Optical materials are actively developed as key materials in the field of optoelectronics such as optical communications and displays, and in the field of energy such as solar cells, and various inorganic glass materials, ceramic materials, laser materials, organic low molecular light emitting materials, Rare earth metal complexes have been created.

  The rare earth metal complex is characterized by absorbing a specific wavelength and emitting light at another wavelength, and is expected to be an excellent wavelength conversion material. In addition to having strong luminescence, the wavelength conversion material also needs high light resistance.

  In recent years, as a strongly luminescent rare earth metal complex, a europium complex (see, for example, Patent Documents 1 and 2) having a β-diketonato and a phosphine oxide ligand has been reported. Although the europium complex disclosed in Patent Document 2 is similar to the europium complex described in the present application, the document is characterized in that it has a substituent at the ortho position of the phenyl group on the phosphorus atom of phosphine oxide. There is no specific description on the europium complex.

RUB 1453860 Unexamined-Japanese-Patent No. 2003-81986

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

  Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, in a europium complex having a β-diketonato and a triphenylphosphine oxide derivative as ligands, the orthoposition of the phenyl group of the triphenylphosphine oxide derivative. It has been found that the light resistance of the europium complex is extremely high when a specific substituent is introduced, and the present invention has been completed.

That is, the present invention
(I) General formula (1)

{Wherein, Z ¹ , Z ² and Z ³ are each independently 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, carbon Groups of 1 to 3 fluoroalkyloxy group, a naphthyl group which may be substituted with a fluorine atom, a pyridyl group which may be substituted with a fluorine atom, or a group represented by the general formula (2)

[Wherein, R ¹ , R ³ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl having 1 to 3 carbon atoms A group, a fluoroalkyloxy group having 1 to 3 carbon atoms, a phenyl group which may be substituted with a fluorine atom, a hydroxyl group or a cyano group. Each of R ² and R ⁴ independently represents a hydrogen atom or a fluorine atom. Represents]. However, Z ¹ , Z ² and Z ³ can not simultaneously be hydrogen atoms. Each of W ¹ and W ² independently represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a phenyl group, a 2-thienyl group or a 3-thienyl group. } Europium complexes as shown;
(Ii) The europium complex according to the above (i), wherein W ¹ and W ² are each independently a fluoroalkyl group having 1 to 6 carbon atoms;
(Iii) each of Z ¹ , Z ² and Z ³ independently represents a hydrogen atom, a methyl group, a methyloxy group, or a group represented by the general formula (2) [in the general formula (2), R ¹ , R ³ and R ⁵ each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyl having 1 to 3 carbon atoms R ² and R ⁴ are a hydrogen atom or an oxy group or a phenyl group. ] The europium complex as described in said (i) or (ii) which is said;
(Iv) General formula (1) has the following formulas 1-1 to 1-7, 1-22, 1-23.

The europium complex according to any one of the above (i) to (iii), which is one compound selected from the group consisting of
(V) An optical material comprising the europium complex according to any one of the above (i) to (iv);
(Vi) The optical material as described in the above (v), which comprises the europium complex as described in any one of the above (i) to (iv) and a resin material;
(Vii) A wavelength conversion material characterized by using the optical material according to (v) or (vi) above;
It is about

  The present invention will be described in detail below.

The definitions of Z ¹ , Z ² , Z ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , W ¹ and W ² in the europium complex (1) of the present invention will be described.

The Z ^1, an alkyl group having 1 to 3 carbon atoms represented by Z ² and Z ³ in the general formula (1) may be linear or branched alkyl group, a methyl group, an ethyl group, a propyl group And isopropyl groups can be exemplified.

The Z ^1, alkyloxy group having 1 to 3 carbon atoms represented by Z ² and Z ³ in the general formula (1) may be linear or branched alkyl group, a methyloxy group, ethyloxy group , A propyloxy group, and a 1-methylethyloxy group can be exemplified.

The fluoroalkyl group having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (1) may be either a linear or branched fluoroalkyl group, a trifluoromethyl group, difluoro group Methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, perfluoropropyl, 2,2,3,3,3-pentafluoro Propyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 1,1-difluoropropyl, 1,1,1,2,3,3,3-hexa A fluoro-2-propyl group, a 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group etc. can be illustrated.

The fluoroalkyloxy group having 1 to 3 carbon atoms represented by Z ¹ , Z ² and Z ³ in the general formula (1) may be either a linear or branched fluoroalkyloxy group, and trifluoromethyloxy Group, difluoromethyloxy group, perfluoroethyloxy group, 2,2,2-trifluoroethyloxy group, 1,1-difluoroethyloxy group, 2,2-difluoroethyloxy group, perfluoropropyloxy group, 2,2 , 3,3,3-pentafluoropropyloxy group, 2,2,3,3-tetrafluoropropyloxy group, 3,3,3-trifluoropropyloxy group, 1,1-difluoropropyloxy group, 1,3 1,1,2,3,3,3-hexafluoro-2-propyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) An ethyloxy group etc. can be illustrated.

As a naphthyl group which may be substituted by the fluorine atom represented by Z < ¹ >, Z < ² > and Z < ³ > of General formula (1), 1-naphthyl group, 2-naphthyl group, 2-fluoro naphthalene -1- yl Group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalen-1-yl group, 1-fluoronaphthalen-2-yl group, 4-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group And 1,3,4,5,6,7,8-heptafluoronaphthalen-2-yl group and the like can be exemplified.

As a pyridyl group which may be substituted by the fluorine atom represented by Z < ¹ >, Z < ² > and Z < ³ > of General formula (1), 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-fluoro Pyridin-6-yl group, 3,5-difluoropyridin-6-yl group, 5-fluoropyridin-6-yl group, 4-fluoropyridin-6-yl group, 3-fluoropyridin-6-yl group, 2 -Fluoropyridin-5-yl group, 2,3-difluoropyridin-5-yl group, 3-fluoropyridin-5-yl group, 4-fluoropyridin-5-yl group, 2-fluoropyridin-3-yl group 2-fluoropyridin-4-yl group, 2,3,5,6-tetrafluoropyridin-4-yl group, 3-fluoropyridin-4-yl group, 3,5-difluoropyridin-4-yl group, 2,6-di Examples include fluoropyridin-3-yl group, 2,5-difluoropyridin-3-yl group, 2,5-difluoropyridin-4-yl group and the like.

^R 1 in the general formula (2), as ^{R 3} and an alkyl group having 1 to 3 carbon atoms represented by ^{R 5,} Z 1, ^{Z 2} and ^{Z 3} of the illustrated alkyl of 1 to 3 carbon atoms in the description The same thing as a group can be illustrated.

Formula (2) As ^R 1, an alkyl group having 1 to 3 carbon atoms represented by ^{R 3} and ^{R 5 of,} Z 1, ^{Z 2} and 1 to 3 carbon atoms exemplified by the description of ^{Z 3} The same thing as an alkyl oxy group can be illustrated.

Formula (2) As ^R 1, a fluoroalkyl group having 1 to 3 carbon atoms represented by ^{R 3} and ^{R 5 of,} Z 1, ^{Z 2} and 1 to 3 carbon atoms exemplified by the description of ^{Z 3} The same as the fluoroalkyl group can be exemplified.

The ^R 1, ^{R 3} and fluoroalkyl group having 1 to 3 carbon atoms represented by ^{R 5} in the general formula ^{(2), Z 1, Z} 2 and illustrated fluoro having 1 to 3 carbon atoms at ^{Z 3} The same thing as an alkyl oxy group can be illustrated.

As a phenyl group which may be substituted by the fluorine atom represented by R < ¹ >, R < ³ > and R < ⁵ > of General formula (2), a phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluoro Phenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 2,4,6-triyl A fluorophenyl group, 3,4,5-trifluorophenyl group, a perfluorophenyl group etc. can be illustrated.

As a substituent represented by R ¹ , R ³ and R ⁵ in the general formula (2), a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms from the viewpoint of good light resistance An oxy group, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyl oxy group having 1 to 3 carbon atoms, or a phenyl group is preferable, and a hydrogen atom, a fluorine atom, a trifluoromethyl group or a trifluoromethyloxy group is more preferable. .

R ² and R ^{4 in} the general formula (2) are a hydrogen atom or a fluorine atom, and a hydrogen atom is preferable in terms of easy availability.

As a substituent represented by Z ¹ , Z ² and Z ³ in the general formula (1), it is substituted by a linear alkyl group, a linear alkyloxy group, a biphenylyl group or a fluorine atom in terms of good light resistance Preferred is a phenyl group, a phenyl group which may be substituted by a linear fluoroalkyl group, or a phenyl group which may be substituted by a linear fluoroalkyloxy group, and a methyl group, a methyloxy group, 4-fluorophenyl Further preferred is a group, 4-trifluoromethylphenyl group or 4-trifluoromethyloxyphenyl group.

The alkyl group having 1 to 6 carbon atoms represented by W ¹ and W ² in the general formula (1) may be any of linear, branched and cyclic alkyl groups, and more specifically methyl group and ethyl group , Propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, isopentyl, neopentyl, tert- Pentyl, cyclopentyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1 , 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, cyclohexyl, cyclic It can be exemplified Penchirumechiru group.

The C ¹ to C 6 fluoroalkyl group represented by W ¹ and W ² in the general formula (1) may be a linear, branched or cyclic fluoroalkyl group, and may be a trifluoromethyl group or difluoromethyl group. Group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl Group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, 1,1,1,2,3,3,3-hexafluoro group -2-propyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1- (trifluoromethyl) propyl group, 1- (trifluoromethyl) propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl Group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2 2,2,3,3-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, 4, 3 , 4,4-octafluoro-2- (trifluoromethyl) butyl group, 1,1,2,2,2,3,4,4,4-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, perfluoro A cyclopentyl group, a 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- (tri) Fluoromethyl) pentyl group, 1,1,2,2,3,3,4 5,5,5-decafluoro-4- (trifluoromethyl) pentyl group, 2,2,3,3,4,4,4-heptafluoro-1,1-bis (trifluoromethyl) butyl group, 1 2,2,3,3,4,4,4-heptafluoro-1,2-bis (trifluoromethyl) butyl group, 1,2,2,3,4,4,4-heptafluoro-1,3- Bis (trifluoromethyl) butyl group, 1,1,3,3,4,4,4-heptafluoro-2,2-bis (trifluoromethyl) butyl group, 1,2,2,3,4,4 , 4-heptafluoro-2,3-bis (trifluoromethyl) butyl group, 1,1,2,2,4,4,4-heptafluoro-3,3-bis (trifluoromethyl) butyl group, perfluoro Examples include cyclohexyl and perfluorocyclopentylmethyl Rukoto can.

Examples of the substituent represented by W ¹ and W ² in the general formula (1), in terms of good light resistance, preferably perfluoroalkyl group having 1 to 6 carbon atoms, trifluoromethyl group, perfluoroethyl group, and perfluoropropyl Groups are more preferred.

  Specific examples of the europium complex (1) of the present invention include the structures shown in the following (1-1) to (1-23), but the present invention is not limited thereto. .

Among the compounds represented by (1-1) to (1-23), as the europium complex (1) of the present invention, (1-1) to (1-7) and (1-11) can be used in terms of good light resistance. ) To (1-18), (1-22) and (1-23) are preferable, and (1-1) to (1-7), (1-22) and (1-23) are more preferable.

  Next, the method for producing the europium complex (1) of the present invention will be described. The europium complex (1) of the present invention can be produced according to step 1 in which a europium salt, β-diketone (3) and phosphine oxide (4) are reacted.

(Step 1)
^{(Wherein, Z 1, Z 2, Z 3} , W 1 and ^{W 2} represent the same meaning as ^{Z 1, Z 2, Z 3} , W 1 and ^{W 2} in the general formula (1).)
Step 1 is a method for producing the europium complex (1) of the present invention by reacting europium salt, β-diketone (3) and phosphine oxide (4), for example, Chemical Communication, Volume 5, 520. By applying the synthesis conditions described on page 521, 2002, the europium complex (1) of the present invention can be obtained with high yield.

  The europium salt used in step 1 is not particularly limited, and examples thereof include halides such as europium fluoride (III), europium chloride (III), europium bromide (III), europium iodide (III) and the like. Salts and hydrates thereof, europium oxalate (III), europium acetate (III), europium trifluoroacetate (III), organic salts such as europium methanetrifluorosulfonate (III) and their hydrates, Metal alkoxides such as tris [N, N-bis (trimethylsilyl) amide] europium (III), europium (III) trimethoxide, europium (III) triethoxide, europium (III) tri (2-propoxide), europium phosphate (III) ), Sulfuric acid Yu Piumu (III), may be mentioned inorganic acid salts and their hydrates, such as europium nitrate (III). Among them, europium chloride (III), europium nitrate (III) or europium oxalate (III), europium acetate (III), europium trifluoroacetate (III), europium methanetrifluorosulfonate (III), in terms of a good reaction yield. And the like are preferable, and europium acetate (III), europium chloride (III), and europium nitrate (III) are more preferable.

  The phosphine oxide (4) used in Step 1 can be obtained by the method described in Reference Example 3 of the present specification or the method described in Chemical Reviews, Volume 60, pages 243-260, 1960, and the like.

  Specific examples of the phosphine oxide (4) used in Step 1 include the structures shown in the following (4-1) to (4-11), but the present invention is not limited thereto: Absent.

  Among the compounds represented by (4-1) to (4-11), as the phosphine oxide (4), the compounds represented by (4-1) to (4-3) are preferable in that the raw materials are inexpensive .

  Specific examples of the β-diketone (3) used in Step 1 include hexafluoroacetylacetone (Hhfa), 1,1,1,5,5,6,6,6-octafluoro-2,4-hexanedione, 1,1,5,5-tetrafluoro-2,4-pentanedione, 1,1,1,2,2,3,3,7,7,8,8,9,9,9,9,9-tetradecafluoro- 4,6-nonanedione (Htdfn), 8H, 8H-perfluoropentadecane-7,9-dione, trifluoroacetylacetone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro- 3,5-octanedione, acetylacetone, 4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione , 1,3-di It can be exemplified Eniru-1,3-dione, etc., but the present invention is not limited thereto. The β-diketone (3) used in Step 1 can be obtained, for example, by the method described in Journal of the American Chemical Society, 66, 1220-1222, 1944 and the like. Alternatively, commercially available products may be used. The β-diketone (3) has an active hydrogen ion, and the hydrogen ion is lost to form an anionic ligand. For example, hfa represents an anionic ligand in which hydrogen ions are lost from Hhfa, and tdfn represents an anionic ligand in which hydrogen ions are lost from Htdfn.

  The production method shown in Step 1 is preferably carried out in a solvent in terms of a good yield of the europium complex (1) of the present invention. There is no particular limitation on the type of solvent that can be used as long as the reaction is not inhibited. Examples of usable solvents include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, alcohols such as methanol, ethanol, propanol and isopropanol, esters such as ethyl acetate, butyl acetate and isoamyl acetate, ethylene glycol mono Glycol ethers such as ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl ether, tert-butyl methyl ether, glyme, diglyme, triglyme, ethers such as tetrahydrofuran, tert-butyl methyl ketone, isobutyl methyl ketone, ethyl Ketones such as butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, acetone etc., hexane, cyclohexane, ethyl Cyclohexane, heptane, octane, benzene, toluene, hydrocarbons such as xylene, and water. Among these solvents, one type can be used alone, and a plurality of types can be mixed and used in an arbitrary ratio. As a solvent, dichloromethane, chloroform, methanol or ethanol is preferable in that the yield of the europium complex (1) of the present invention is good.

  Next, the molar ratio of europium salt and phosphine oxide (4) when carrying out the production method represented by step 1 will be described. It is preferable to use 0.5 to 5.0 mol, more preferably 1.0 to 2.5 mol of phosphine oxide (4) per 1 mol of europium salt.

  It demonstrates with respect to the molar ratio of the europium salt and (beta) -diketone (3) when implementing the manufacturing method represented by the process 1. FIG. 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 production method represented by step 1, the reaction temperature and the reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, the europium complex (1) of the present invention can be obtained by selecting the reaction time appropriately selected from the range of 1 minute to 120 hours at the reaction temperature appropriately selected from the temperature range of -80 to 120 ° C. It can be manufactured well.

  The europium complex (1) of the present invention produced by the production method represented by the step 1 can be purified by appropriately selecting and using a general purification method when a person skilled in the art refines a metal complex. Specific purification methods may include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  Moreover, the europium complex (1) of this invention can also be manufactured according to the process 2 which makes diketonato complex (5) and phosphine oxide (4) react.

(Step 2)
^{(Wherein, Z 1, Z 2, Z} 3, W 1 and ^{W 2 Z 1, Z 2, Z 3} , W represents the same meaning as ¹ and ^{W 2} .Q is coordinated molecules of the general formula (1) And m represents a number of 0 to 3.)
Step 2 is a step of producing the europium complex (1) of the present invention by reacting phosphine oxide (4) with diketonato complex (5), for example, Applied Physics Letters, vol. 83, 3599-3601. The europium complex (1) of the present invention can be obtained in good yield by applying the synthesis conditions described in J. Chem., 2003.

  The coordination molecule represented by Q is not limited as long as it does not inhibit the reaction, and specifically, water, heavy water, tetrahydrofuran, pyridine, imidazole, acetone, methanol, ethanol, propanol, isopropyl alcohol, acetonitrile or propio Examples thereof include nitriles such as nitrile, amines such as ammonia, diethylamine and triethylamine, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, and the like, and water is preferable in that the synthesis of the diketonato complex (5) is easy.

  M of the diketonato complex (5) represents a number of 0 to 3, preferably 2 in view of easy availability.

  The diketonato complex (5) used in Step 2 is obtained by the method described in Reference Example 1 of the present specification or the method described in Journal of the American Chemical Society, vol. 87, pages 5254-5256, 1965, etc. Can.

  Specific examples of the diketonato complex (5) used in step 2 include tris (hexafluoroacetylacetonato) europium (III), tris (1,1,1,5,5,6,6,6-octafluoro) -2,4-dioxohexan-3-oid) europium (III), tris (1,1,5,5-tetrafluoro-2,4-dioxopentan-3-id) europium (III), tris (III) 1,1,1,2,2,2,3,3,7,7,8,8,9,9,9,9-tetradecafluoro-4,6-dioxononan-5-ide) europium (III), tris (1 1, 1, 2, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 10, 11, 11, 12, 12, 13, 13, 14, 14, 15, 15, 15 -Hexacosafluoro-7,9-dioxopentadecane 8-id) europium (III), tris (trifluoroacetylacetonato) europium (III), tris [4,4,4-trifluoro-1- (2-thienyl) -1,3-dioxobutan-2-ide Europium (III), tris (4,4,4-trifluoro-1-phenyl-1,3-dioxobutan-2-ide) europium (III), tris (1,3-diphenyl-1,3-dioxo) Although propan-2-oids) europium (III) and their hydrates can be exemplified, the present invention is not limited thereto.

  The phosphine oxide (4) used in Step 2 is the method described in Reference Example 3 of the present specification, Chemical Reviews, Volume 60, pages 243-260, 1960 and Organic Letters, Volume 13, pages 3478-3481, etc. It can be obtained by the method described in

  As the phosphine oxide (4) used in the step 2, although the same one as exemplified in the description of the step 1 can be exemplified, the present invention is not limited thereto.

  The production method shown in step 2 is preferably carried out in a solvent in terms of a good yield of the europium complex (1) of the present invention. There is no particular limitation on the type of solvent that can be used as long as the reaction is not inhibited. Examples of usable solvents include halogen-based 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, and ethylene glycol Glycol ethers such as monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl ether, tert-butyl methyl ether, ethers such as glyme, diglyme, triglyme, tetrahydrofuran, tert-butyl methyl ketone, isobutyl methyl ketone Ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, ketones such as cyclohexanone and acetone, hexane, cyclohexane, Chill cyclohexane, heptane, octane, benzene, toluene, hydrocarbons such as xylene, and water. Among these solvents, one type can be used alone, and a plurality of types can be mixed and used in an arbitrary ratio. As a solvent, dichloromethane, chloroform, methanol or ethanol is preferable in that the yield of the europium complex (1) of the present invention is good.

  Next, the molar ratio of diketonato complex (5) and phosphine oxide (4) when carrying out the production method represented by step 2 will be described. It is preferable to use 0.5 to 5.0 moles, more preferably 1.0 to 2.5 moles of phosphine oxide (4) per 1 mole of diketonato complex (5).

  In the production method represented by step 2, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, the europium complex (1) of the present invention can be obtained by selecting the reaction time appropriately selected from the range of 1 minute to 120 hours at the reaction temperature appropriately selected from the temperature range of -80 to 120 ° C. It can be manufactured well.

  The europium complex (1) of the present invention produced by the production method represented by step 2 can be purified by appropriately selecting and using a general purification method when a person skilled in the art refines a metal complex. Specific purification methods may include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  Since the europium complex (1) of the present invention has excellent light resistance, it is preferable to use the optical material containing the europium complex (1) of the present invention, and examples of the optical material include sunlight and ultraviolet light. It is difficult to deteriorate even when irradiated for a long time, and wavelength conversion materials such as films for solar cells, films for agriculture, LED phosphors, security inks and the like are preferably useful.

  In addition, the europium complex (1) of the present invention can be used as an optical material containing one or more kinds selected from resin materials, inorganic glasses, and organic low molecular weight materials, and since the dispersibility is high, optical materials containing resin materials It is particularly preferable to Examples of the resin material include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, poly sec-butyl methacrylate, polyisobutyl methacrylate, poly tert-butyl methacrylate, fluorine-containing polymethyl methacrylate, and fluorine-containing resin Polyethyl methacrylate, fluorine-containing polypropyl methacrylate, fluorine-containing polyisopropyl methacrylate, fluorine-containing polybutyl methacrylate, fluorine-containing poly sec-butyl methacrylate, fluorine-containing polyisobutyl methacrylate, fluorine-containing poly tert-butyl methacrylate, polymethacrylates, polymethyl Acrylate, polyethyl acrylate, polypropyl acrylate, poly Propyl acrylate, polybutyl acrylate, poly sec-butyl acrylate, polyisobutyl acrylate, poly tert-butyl acrylate, fluorine-containing polymethyl acrylate, fluorine-containing polyethyl acrylate, fluorine-containing polypropyl acrylate, fluorine-containing polyisopropyl acrylate, fluorine-containing poly Polyacrylates such as butyl acrylate, fluorine-containing poly sec-butyl acrylate, fluorine-containing poly isobutyl acrylate, fluorine-containing poly tert-butyl acrylate, polystyrene, polyethylene, polypropylene, polybutene, fluorine-containing polyethylene, fluorine-containing polypropylene, fluorine-containing polybutene, etc. Polyolefin, polyvinyl ether, fluorine-containing polyvinyl ether, polyvinyl acetate, polyvinyl chloride And copolymers thereof, cellulose, polyacetal, polyester, polycarbonate, epoxy resin, polyamide resin, polyimide resin, polyurethane, Nafion, petroleum resin, rosin, silicon resin, etc., among which polymethyl methacrylate, polyethyl methacrylate, Polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, poly sec-butyl methacrylate, polyisobutyl methacrylate, poly tert-butyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, poly sec -Butyl acrylate, polyisobutyl acrylate, poly tert-butyl acrylate , Polyethylene, polystyrene, polyvinyl acetate and copolymers thereof and the like are preferable, and polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, Polyethylene, polystyrene, polyvinyl acetate and their copolymers are particularly preferred. These may be used alone or in combination of two or more.

  Among these resin materials, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polystyrene, polyvinyl acetate and the like, which are particularly preferably used The polymer is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, styrene or vinyl acetate as a resin material at 50 to 80 ° C. in the presence of a polymerization initiator. It can be obtained by carrying out suspension polymerization in water for 3 to 8 hours.

  The polymerization initiator to be used may be one commonly used by those skilled in the art when polymerizing these resin materials. For example, azo compounds such as azobisisobutyro nitrile, potassium persulfate, ammonium persulfate, benzoyl peroxide and the like Organic peroxides can be mentioned.

  In the case of suspension polymerization, in order to prevent aggregation of the polymer particles obtained, it is preferable to add a dispersion stabilizer, which may be one commonly used by those skilled in the art as the dispersion stabilizer, for example, basic calcium phosphate, water Examples thereof include poorly water-soluble inorganic fine particles such as aluminum oxide and magnesium carbonate, polyacrylates, polymethacrylates, polyacrylamides, polyvinyl alcohols and cellulose derivatives.

  In the case of suspension polymerization, in order to prevent suppression of gelation, it is preferable to add a polymerization regulator, and a person skilled in the art may usually use as the polymerization regulator, for example, 4-hydroxy-2, Examples thereof include nitroxyl compounds such as 2,6,6-tetramethylpiperidin-1-oxyl, nitrites such as sodium nitrite, and nitrogen oxides such as di-tert-butyl nitroxide.

The proportion of the europium complex (1) in the optical material containing the europium complex (1) of the present invention and the resin material is preferably 0.001 to 99% by weight, more preferably 0.01 to 10% by weight.
The inorganic glass may be one commonly used by those skilled in the art, and examples thereof include soda glass, crystal glass, borosilicate glass and the like.
The organic low molecular weight material may be one commonly used by those skilled in the art, for example, ionic liquids such as amyl triethyl ammonium bis (trifluoromethane sulfonyl) imide and tetra amyl ammonium chloride, pentadecane, hexadecane, octadecane, nonadecane, icosane, paraffin, etc. Hydrocarbons and the like.

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

  When the europium complex (1) of the present invention is dissolved and dispersed in a solvent to make an optical material, examples of the solvent that can be used include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, methanol, ethanol, propanol, Alcohols such as isopropyl alcohol, Esters such as ethyl acetate, butyl acetate, isoamyl acetate, Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethyl ether, tert-butyl methyl ether, Ethers such as glyme, diglyme, triglyme, tetrahydrofuran, tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, Sobuchiruketon, cyclohexanone may be mentioned ketones such as acetone, hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, toluene, hydrocarbons such as xylene, and water. These solvents may be used alone or in combination of two or more in any ratio.

  The europium complex (1) of the present invention becomes a compound having excellent light resistance by introducing a specific substituent at the ortho position of the phenyl group on the phosphorus atom of the phosphine oxide, and it can be used for a long time for sunlight and ultraviolet light. Since it is difficult to deteriorate even when irradiated and has high light resistance, it becomes a promising wavelength conversion material that can be used for a long time.

FIG. 2 is a crystal structure of bis [(2-biphenylyl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato) europium (III) obtained in Example 1. FIG. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 1. FIG. 6 is an emission spectrum of the europium complex (1) of the present invention obtained in Example 2. FIG. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 3. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 4. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 5. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 6. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 7. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 8. It is an emission spectrum of the europium complex (1) of the present invention obtained in Example 9. It is an emission spectrum of an optical material containing the europium complex (1) of the present invention obtained in Example 10. It is an emission spectrum of the optical material containing the europium complex (1) of the present invention obtained in Example 11. It is a light resistance test evaluation result of the europium complex obtained by Comparative Examples 1-3. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 1. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 2. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 3. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 4. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 5. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 6. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 7. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 8. FIG. It is a light resistance test evaluation result of the europium complex (1) of this invention obtained in Example 9. FIG.

  Hereinafter, the present invention will be described in more detail by way of Examples, Comparative Examples and Evaluation Examples, but the present invention is not construed as being limited thereto.

  The following analysis methods were used to identify the europium complex (1) of the present invention.

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

  The measurement of mass spectrometry was performed using waters 2695-micromass ZQ4000 manufactured by waters.

  The elemental analysis used MICRO-CORDER JM10 by J. Science Labs.

  For single crystal X-ray crystal structure analysis, the obtained single crystal was mounted on a gonio head, and measurement was performed using a RIGAKU R-AXIS RAPID II apparatus. Details of the analysis conditions are shown below.

<Analytical conditions>
X-ray source: CuKα (λ = 1.54187 Å)
Detector: Imaging plate The measurement of the emission spectrum was performed using a spectrophotometer (FP-6500, manufactured by JASCO Corporation).

  The luminescence quantum yield was measured using an absolute PL quantum yield measurement apparatus (C9920-03 manufactured by Hamamatsu Photonics K.K.).

  Moreover, the reagents used the commercial item.

  Reference Example 1

Under an argon atmosphere, pure water (100 mL) was added to europium acetate n hydrate (8.0 g, 21 mmol as 2.5 hydrate), and the mixture was stirred at room temperature for 10 minutes. After Hhfa (16.7 g, 80.2 mmol) was added dropwise to the reaction mixture, the mixture was stirred at 50 ° C. for 3 hours. The obtained white suspension was filtered off, and the obtained 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 as 21 mmol of europium acetate n hydrate were used). ¹⁹ F-NMR (376 MHz, Acetone-d ₆ ), δ (ppm): -81.2 (brs). ESIMS (m / z): 566.8 [M-hfa] ^<+> .

  Reference Example 2

Under an argon atmosphere, 2-bromobiphenyl (1.40 g, 6.00 mmol) was dissolved in diethyl ether (10 mL) and cooled to -15.degree. To this solution, a 2.67 M hexane solution (2.4 mL, 6.41 mmol) of n-butyllithium was added dropwise, and after stirring for 2 hours, a 0.54 M solution of chlorodiphenylphosphine in diethyl ether (10 mL, 5.4 mmol) was added. In addition, the mixture was stirred for 3 hours while slowly warming to room temperature. The reaction solution is filtered, the filtrate is concentrated under reduced pressure, and the obtained crude product is purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a white solid of (2-biphenylyl) diphenylphosphine. Obtained (yield 1.6 g, yield 79%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.41 to 7.37 (m, 1 H), 7.34 to 7.16 (m, 17 H), 7.07 to 7.04 (m m, 1 H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): −13.5 (s).

(2-Biphenylyl) diphenylphosphine (341 mg, 1.01 mmol) was dissolved in dichloromethane (5 mL), to which 30% aqueous hydrogen peroxide (2.4 mL) was added, and stirred at room temperature for 3.5 hours. Water (15 mL) was added to the reaction mixture, the organic layer was separated, chloroform (15 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of (2-biphenylyl) diphenylphosphine oxide (yield 300 mg, 84%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.59 to 7.53 (m, 5 H), 7.44 to 7.28 (m, 9 H), 7.22 to 7.19 ( m, 2H), 7.07-7.02 (m, 3H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 27.8 (s).

  Reference Example 3

In an argon atmosphere, 3-bromo-2,2'-biphenyl (280 mg, 1.20 mmol), nickel chloride hexahydrate (23.8 mg, 0.10 mmol), 2,2'-bipyridyl (31.2 mg, 0) 20 mmol), zinc powder (131 mg, 2.00 mmol) and diphenylphosphine oxide (202 mg, 1.00 mmol) were suspended in water (2.0 mL) and stirred at 70 ° C. for 16 hours. The reaction mixture was charged with chloroform (4.0 mL) and water (2.0 mL), filtered, and the residue was washed with chloroform. The filtrate was separated, and the aqueous layer was extracted with chloroform (10 mL × 2), and the combined organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain (3-biphenylyl) diphenylphosphine oxide (316 mg, yield 89%) as a white solid. ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.95 (brd, J = 12.6 Hz, 1 H), 7.77 (brd, J = 7.6 Hz, 1 H), 7.75- 7.67 (m, 4 H), 7.63 to 7.39 (m, 12 H), 7. 35 (brdd, J = 7.3, 7.3 Hz, 1 H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 29.1 (s).

  Reference Example 4

In an argon atmosphere, 4-bromo-2,2'-biphenyl (280 mg, 1.20 mmol), nickel chloride hexahydrate (23.8 mg, 0.10 mmol), 2,2'-bipyridyl (31.2 mg, 0) 20 mmol), zinc powder (131 mg, 2.00 mmol) and diphenylphosphine oxide (202 mg, 1.00 mmol) were suspended in water (2.0 mL) and stirred at 70 ° C. for 16 hours. The reaction mixture was charged with chloroform (4.0 mL) and water (2.0 mL), filtered, and the residue was washed with chloroform. The filtrate was separated, and the aqueous layer was extracted with chloroform (10 mL × 2), and the combined organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain (4-biphenylyl) diphenylphosphine oxide (344 mg, yield 97%) as a white solid. ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.77 to 7.66 (m, 8 H), 7.63 to 7.53 (m, 4 H), 7.52 to 7.43 (m m, 6H), 7.39 (brdd, J = 7.3, 7.3 Hz, 1 H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 29.0 (s).

  Reference Example 5

Tri (o-tolyl) phosphine (1.01 g, 3.03 mmol) was dissolved in dichloromethane (10 mL), 30% aqueous hydrogen peroxide (1.0 mL) was added, and the mixture was stirred at room temperature for 2.5 hours. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (10 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over magnesium 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 448 mg, 42%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.43 (brdd, J = 7.5, 7.4 Hz, 3 H), 7.32 (brdd, J = 7.5, 4.1 Hz) , 3H), 7.19 to 7.05 (m, 6H), 2.50 (s, 9H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 37.1 (s).

  Reference Example 6

Tris (2-methoxyphenyl) phosphine (2.00 g, 5.68 mmol) was dissolved in dichloromethane (20 mL), 30% aqueous hydrogen peroxide (3.5 mL) was added, and the mixture was stirred at room temperature for 1 hour. Water (60 mL) was added to the reaction mixture, the organic layer was separated, chloroform (50 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 a white solid of tris (2-methoxyphenyl) phosphine oxide (yield 1.85 g, 88%) ). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.54 to 7.43 (m, 6 H), 6.98 (td, J = 7.6, 2.3 Hz, 3 H), 6. 90 (dd, J = 5.3, 2.3 Hz, 3 H), 3.57 (s, 9 H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 25.6 (s).

  Reference Example 7

1-bromo-2-iodobenzene (7.23 g, 25.6 mmol), diphenylphosphine (4.71 g, 25.3 mmol), palladium (II) acetate (30.4 mg, 0.135 mmol) and acetic acid under an argon atmosphere N, N-dimethylacetamide (55.0 mL) was added to sodium (2.28 g, 27.8 mmol) and stirred at 130 ° C. for 3 days. The reaction mixture was poured into water (100 mL), and the aqueous layer was extracted twice with chloroform (60 mL). The combined organic layer was washed with 100 mL of water four times, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a white solid of (2-bromophenyl) diphenylphosphine (yield 6.07 g, 70% yield) ). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.59 (m, 1 H), 7.38 to 7.32 (m, 6 H), 7.30 to 7.25 (m, 4 H) , 7.21 to 7.16 (m, 2H), 6.76 (m, 1H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -5.1 (s).

After dissolving (2-bromophenyl) diphenyl phosphine (6.07 g, 17.8 mmol) in dichloromethane (35 mL) and cooling to 0 ° C., 30% aqueous hydrogen peroxide (10 mL) is added and stirred at room temperature for 1 hour did. Water (20 mL) was added to the reaction mixture, the organic layer was separated, chloroform (50 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 crude product obtained is purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain (2-bromophenyl) diphenylphosphine oxide (yield 6.00 g, 94%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.74 to 7.66 (m, 5 H), 7.59 to 7.7. 55 (m, 2 H), 7.5 1 to 7. 46 (m, 4H), 7.41 to 7.32 (m, 3H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 30.5 (s).

  Reference Example 8

(2-bromophenyl) diphenylphosphine oxide (500 mg, 1.40 mmol) obtained in Reference Example 7 under an argon atmosphere, 4-fluorophenylboronic acid (196 mg, 1.40 mmol), triphenylphosphine (44 mg, 0.168 mmol) 1,4-dioxane (5.0 mL) is added to tripotassium phosphate (590 mg, 2.78 mmol) and bis (dibenzylideneacetone) palladium (0) (24 mg, 0.0417 mmol), and the reaction is carried out at 100 ° C. for 14 hours. It stirred. Water (30 mL) was added to the reaction mixture, chloroform (20 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product is purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give a white solid of (4'-fluoro [1,1'-biphenyl] -2-yl) diphenylphosphine oxide (Yield 431 mg, yield 83%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.59 to 7.53 (m, 5 H), 7.43 to 7.29 (m, 9 H), 7.18 (dd, J =) 8.6, 5.2 Hz, 2 H), 6.73 (t, J = 8.6 Hz, 2 H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −115.5 (s) ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 27.7 (s).

  Reference Example 9

(2-bromophenyl) diphenylphosphine oxide (500 mg, 1.40 mmol), 4- (trifluoromethyl) phenylboronic acid (266 mg, 1.40 mmol), triphenylphosphine (44 mg) obtained in Reference Example 7 under an argon atmosphere Add 1,4-dioxane (5.0 mL) to tripotassium phosphate (590 mg, 2.78 mmol) and bis (dibenzylideneacetone) palladium (0) (24 mg, 0.0417 mmol), and add 100 Stir at <RTIgt; C </ RTI> for 14 hours. Water (30 mL) was added to the reaction mixture, chloroform (20 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The resulting crude product is purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give (4'-trifluoromethyl [1,1'-biphenyl] -2-yl) diphenylphosphine oxide A white solid was obtained (yield 413 mg, 70%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.60 to 7.54 (m, 5 H), 7.46 to 7.36 (m, 4 H), 7.34 to 7.27 ( m, 9H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -62.8 (s) ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 27.2 (s).

  Reference Example 10

(2-bromophenyl) diphenylphosphine oxide (500 mg, 1.40 mmol) obtained in Reference Example 7 under an argon atmosphere, 4- (trifluoromethoxy) phenylboronic acid (288 mg, 1.40 mmol), triphenylphosphine (44 mg) 1,4-dioxane (5.0 mL) was added to tripotassium phosphate (590 mg, 2.78 mmol) and bis (dibenzylideneacetone) palladium (0) (24 mg, 0.042 mmol), Stir at <RTIgt; C </ RTI> for 14 hours. Water (30 mL) was added to the reaction mixture, chloroform (20 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The resulting crude product is purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give (4'-trifluoromethoxy [1,1'-biphenyl] -2-yl) diphenylphosphine oxide A white solid was obtained (yield 157 mg, 26%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.60 to 7.55 (m, 5 H), 7.43 to 7.24 (m, 11 H), 6.88 (d, J = 8.1 Hz, 2 H). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -57.7 (s) ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 27.3 (s).

  Reference Example 11

Dissolve diphenyl (o-tolyl) phosphine (1.00 g, 3.62 mmol) in dichloromethane (5.0 mL) and cool to 0 ° C., then add 30% aqueous hydrogen peroxide (2.0 mL) and room temperature Stir for 1 hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (20 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of diphenyl (o-tolyl) phosphine oxide (yield 948 mg, 90%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.68 to 7.62 (m, 4 H), 7.57 to 7.52 (m, 2 H), 7.49 to 7.39 ( m, 5H), 7.30 to 7.27 (m, 1H), 7.16 to 7.10. (m, 1H), 7.06 to 6.99 (m, 1H), 2.45 (s, 5) 3H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 31.5 (s).

  Reference Example 12

Dissolve diphenyl (2-methoxyphenyl) phosphine (1.08 g, 3.68 mmol) in dichloromethane (5.0 mL) and cool to 0 ° C., then add 30% aqueous hydrogen peroxide (2.0 mL) and room temperature The mixture was stirred for 1 hour. Water (10 mL) was added to the reaction mixture, the organic layer was separated, chloroform (20 mL) was added to the aqueous layer, and the chloroform layer was separated. This operation was repeated twice. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform / methanol) to obtain a white solid of diphenyl (2-methoxyphenyl) phosphine oxide (yield 986 mg, 87%). ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 7.80 to 7.65 (m, 5 H), 7.56 to 7.47 (m, 3 H), 7.46 to 7.39 ( m, 4H), 7.08 (t, J = 7.8 Hz, 1 H), 6.92 (dd, J = 7.8, 5.2 Hz, 1 H), 3.56 (s, 3 H). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): 27.2 (s).

  Example 1

Europium acetate n hydrate (1.12 g, 2.9 mmol as 2.5 hydrate) and (2-biphenylyl) diphenyl phosphine oxide (2.13 g, 6.02 mmol) obtained in Reference Example 2 under an argon atmosphere To the mixture was added dichloromethane (40 mL) and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 2.0 M solution of Hhfa in dichloromethane (4.5 mL, 9.0 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution is filtered, and the filtrate is concentrated under reduced pressure and recrystallized with dichloromethane / hexane to give bis [(2-biphenylyl) diphenylphosphine oxide)] tris (hexafluoroacetylacetonato) europium (III) as a white solid. (Yield 3.09 g, 68% as 2.99 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -76.1 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -92.5 (brs). ESIMS (m / z): 1275.6 [M-hfa] ⁺ . Anal. Calcd. _{for [C 63 H 41 EuF 18} O 8 P 2]: C, 51.06%; H, 2.79%. Found: C, 50.94%; H, 2.90%. In addition, single crystal X-ray structural analysis of bis [(2-biphenylyl) diphenyl phosphine oxide)] tris (hexafluoroacetylacetonato) europium (III) was performed. The results of single crystal X-ray structural analysis are shown below, and the crystal structure obtained thereby is shown in FIG.

Monoclinic (P121)
a = 13.540 (3) Å
b = 11.657 (4) Å
c = 19.191 (8) Å
β = 97.74 (3) °
V = 3001.3 (17) Å ³
Z = 2
R1 = 0.1090
wR2 = 0.3838
Example 2

Under argon atmosphere, dichloromethane (5 mg) was added to europium acetate n hydrate (132 mg, 0.353 mmol as 2.5 hydrate) and tri (o-tolyl) phosphine oxide (256 mg, 0.80 mmol) obtained in Reference Example 5 .0 mL) was added and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 1.8 M solution of Hfac in dichloromethane (0.67 mL, 1.2 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution is filtered, the filtrate is concentrated under reduced pressure, and recrystallization from methanol gives a reddish white solid of bis [tri (o-tolyl) phosphine oxide] tris (hexafluoroacetylacetonato) europium (III). (Yield 364 mg, 73% yield as 0.353 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -79.1 (s). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -104 (brs). ESIMS (m / z): 1207.4 [M-hfa] ^<+> .

  Example 3

Dichloromethane (258 mg, 0.700 mmol) obtained in Reference Example 6 and europium acetate n hydrate (131 mg, 0.350 mmol as 2.5 hydrate) and dichloromethane (258 mg, 0.700 mmol) under an argon atmosphere 5.0 mL) was added and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 2.1 M solution of Hhfa in dichloromethane (0.50 mL, 1.05 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and recrystallized with methanol to obtain a white solid of tris [tris (2-methoxyphenyl) phosphine oxide] tris (hexafluoroacetylacetonato) europium (III) (yield 344 mg, acetic acid) 65% yield as 0.350 mmol of europium n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -78.7 (brs). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 118.5 (brs). ESIMS (m / z): 1303.5 [M-hfa] ⁺ .

  Example 4

In an atmosphere of argon, europium acetate n-hydrate (74.8 mg, 0.200 mmol as 2.5-hydrate) and (2-biphenylyl) diphenylphosphine oxide (142 mg, 0.401 mmol) obtained in Reference Example 2 and dichloromethane (3.0 mL) was added and stirred at room temperature for 1 hour. 1,1,1,2,2,2,3,3,7,7,8,8,9,9,9,9-tetradecafluoro-4,6-nonanedione (0.15 mL, 0.603 mmol) in the reaction mixture After dropping, the mixture was stirred at room temperature for 10 hours. The reaction solution is filtered, the filtrate is concentrated under reduced pressure, and recrystallized with methanol to give bis [(2-biphenylyl) diphenylphosphine oxide] tris (1,1,1,2,2,3,3,7, 7,8,8,9,9,9,9-tetradecafluoro-4,6-dioxononan-5-id) A white solid of europium (III) was obtained (yield 278 mg, 0.200 mmol of europium acetate n hydrate) Yield 67% as used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): −80.9 (brs, 18 F), −123.1 (brs, 12 F), −127.0 (brs, 12 F). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -106.8 (brs). ESIMS (m / z): 1675.5 [M-tdfn] ^<+> .

  Example 5

Europium acetate n hydrate (112 mg, 0.299 mmol as 2.5 hydrate) and (4'-fluoro [1,1'-biphenyl] -2-yl) diphenyl obtained in Reference Example 8 under an argon atmosphere Dichloromethane (4.0 mL) was added to phosphine oxide (223 mg, 0.599 mmol) and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 1.8 M solution of Hhfa in dichloromethane (0.5 mL, 0.90 mmol), and the mixture was stirred at room temperature for 12 hours. The reaction solution is concentrated under reduced pressure and recrystallized with dichloromethane / hexane to give bis [(4′-fluoro [1,1′-biphenyl] -2-yl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato) europium. A bright white solid of (III) was obtained (yield 349 mg, 77% as 0.299 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -79.0 (brs, 18F), -113.6 (brs, 2F). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 92.1 (brs). ESIMS (m / z): 1311.2 [M-hfa] ^<+> .

  Example 6

Europium acetate n-hydrate (112 mg, 0.299 mmol as 2.5-hydrate) under argon atmosphere and obtained in Reference Example 9 (4'-trifluoromethyl [1,1'-biphenyl] -2-yl Dichloromethane (4.0 mL) was added to diphenylphosphine oxide (253 mg, 0.599 mmol) and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 0.9 M solution of Hhfa in dichloromethane (1.0 mL, 0.90 mmol), and the mixture was stirred at room temperature for 6 hours. The reaction solution is concentrated under reduced pressure and recrystallized with acetone / methanol to give bis [(4′-trifluoromethyl [1,1′-biphenyl] -2-yl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato). 2.) A bright white solid of europium (III) was obtained (yield 286 mg, 59% as 0.299 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -62.0 (brs, 6F), -79.1 (brs, 18F). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -91.7 (brs). ESIMS (m / z): 1411.3 [M-hfa] ^<+> .

  Example 7

Europium acetate n-hydrate (56 mg, 0.150 mmol as 2.5-hydrate) under argon atmosphere and (4'-trifluoromethoxy [1,1'-biphenyl] -2-yl obtained in Reference Example 10) Dichloromethane (3.0 mL) was added to diphenylphosphine oxide (132 mg, 0.301 mmol) and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 0.9 M solution of Hhfa in dichloromethane (0.5 mL, 0.45 mmol), and the mixture was stirred at room temperature for 6 hours. The reaction solution is concentrated under reduced pressure and recrystallized with dichloromethane / hexane to give bis [(4′-trifluoromethoxy [1,1′-biphenyl] -2-yl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato). 2.) A bright white solid of europium (III) was obtained (yield 195 mg, 79% yield as 0.150 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -56.7 (brs, 6F), -79.1 (brs, 18F). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -92.5 (brs). ESIMS (m / z): 1443.3 [M-hfa] ^<+> .

  Example 8

Under argon atmosphere, dichloromethane (3 mg) was added to europium acetate n hydrate (112 mg, 0.30 mmol as 2.5 hydrate) and diphenyl (o-tolyl) phosphine oxide (175 mg, 0.60 mmol) obtained in Reference Example 11 .0 mL) was added and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 1.8 M solution of Hhfa in dichloromethane (0.5 mL, 0.90 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and recrystallized with dichloromethane / hexane to give a pale white solid of bis [diphenyl (o-tolyl) phosphine oxide] tris (hexafluoroacetylacetonato) europium (III) (yield: 315 mg) (77% yield as 0.30 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -79.0 (brs). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 92.7 (brs). ESIMS (m / z): 1150.8 [M-hfa] ^<+> .

  Example 9

Under argon atmosphere, dichloromethane (112 mg, 0.30 mmol as 2.5 hydrate) and diphenyl (2-methoxyphenyl) phosphine oxide (185 mg, 0.60 mmol) obtained in Reference Example 12 in dichloromethane (112 mg, 2.5 hydrate as 2.5 hydrate) 3.0 mL) was added and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 1.8 M solution of Hhfa in dichloromethane (0.5 mL, 0.90 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and recrystallized with dichloromethane / hexane to give a bright white solid of bis [diphenyl (2-methoxyphenyl) phosphine oxide] tris (hexafluoroacetylacetonato) europium (III) (yield 334 mg, 80% yield as 0.30 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -78.9 (brs). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 97.8 (brs). ESIMS (m / z): 1183.1 [M-hfa] ^<+> .

Example 10
The bis [(2-biphenylyl) diphenyl phosphine oxide] tris (hexafluoro acetyl acetonato obtained in Example 1 to the toluene solution (4 mL) of Tosoh ethylene-vinyl acetate copolymer resin (Ultracene 720) (889 mg) ) A solution of europium (III) (10 mg) in toluene (1 mL) was added. The mixture is stirred at room temperature for 30 minutes, and the resulting viscous liquid is applied by drop casting to a flat quartz glass substrate surface, and dried for 24 hours at a temperature of 60 ° C. to give bis [(2-biphenylyl) diphenyl Optical materials containing phosphine oxide] tris (hexafluoroacetylacetonato) europium (III) were prepared.

Example 11
Methyl methacrylate monomer (40.1 g, 401 mmol) in an aqueous solution obtained by adding pure water (203 mL) to polyvinyl alcohol (2.38 g) as a dispersion stabilizer and sodium nitrite (0.119 g, 1.7 mmol) as a polymerization regulator ) And benzoyl peroxide (0.795 g, 3.3 mmol) as a polymerization initiator, bis [tri (o-tolyl) phosphine oxide] tris (hexafluoroacetylacetonato) europium (III) (39) obtained in Example 2 .6 mg, 0.028 mmol) of the mixture was added. The mixture is stirred at 65 ° C. for 4 hours, and the resulting white suspension is filtered, washed with pure water, dried by heating under reduced pressure (80 ° C., 2 hours), and bis [tri (o-tolyl) phosphine oxide] An optical material (38.5 g) containing tris (hexafluoroacetylacetonato) europium (III) was prepared.

  Comparative Example 1

Ethanol (200 mL) in diaquatris (hexafluoroacetylacetonato) europium (III) (5.0 g, 6.18 mmol) and triphenylphosphine oxide (3.4 g, 12.4 mmol) obtained in Reference Example 1 under an argon atmosphere Was added and 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, yield 58%). In addition, this compound is a compound concretely described in RUB1453869 and Unexamined-Japanese-Patent No. 2003-81986. ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -79.0 (brs). ³¹ P-NMR (162 MHz, CDCl ₃ ), δ (ppm): -91.3 (brs). ESIMS (m / z): 1123.4 [M-hfa] ^<+> .

  Comparative example 2

In an atmosphere of argon, europium acetate n hydrate (74.8 mg, 0.200 mmol as 2.5 hydrate) and (3-biphenylyl) diphenylphosphine oxide (142 mg, 0.401 mmol) obtained in Reference Example 3 are dichloromethane. (3.0 mL) was added and stirred at room temperature for 1 hour. After adding dropwise a 1.5 M solution of Hhfa in dichloromethane (0.40 mL, 0.60 mmol) to the reaction mixture, the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and recrystallized with methanol to obtain bis [(3-biphenylyl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato) europium (III) as a white solid (yield 164 mg, europium acetate) 55% yield as 0.200 mmol of n-hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -79.0 (brs). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 88.8 (brs). ESIMS (m / z): 1275.6 [M-hfa] ^<+> .

  Comparative example 3

Under argon atmosphere, europium acetate n-hydrate (180 mg, 0.481 mmol as 2.5 hydrate) and (4-biphenylyl) diphenyl phosphine oxide (344 mg, 0.971 mmol) obtained in Reference Example 4 were added with dichloromethane (8 .0 mL) was added and stirred at room temperature for 1 hour. To the reaction mixture was added dropwise a 1.5 M solution of Hhfa in dichloromethane (0.96 mL, 1.44 mmol), and the mixture was stirred at room temperature for 3 hours. The reaction solution is filtered, the filtrate is concentrated under reduced pressure, and recrystallized with methanol to obtain a bright white solid of bis [(4-biphenylyl) diphenylphosphine oxide] tris (hexafluoroacetylacetonato) europium (III). (Yield 465 mg, 65% yield as 0.480 mmol of europium acetate n hydrate was used). ¹⁹ F-NMR (376 MHz, CDCl ₃ ), δ (ppm): -78.9 (brs). ^{31 P-NMR (162MHz, CDCl} 3), δ (ppm): - 91.2 (brs). ESIMS (m / z): 1275.5 [M-hfa] ^<+> .

Evaluation Examples Measurement of emission spectrum of europium complex (1) of the present invention and europium complexes obtained in Comparative Examples 1 to 3 and samples for evaluation of light resistance were the europium complexes (1) synthesized in Examples 1 to 9 and The powder of the europium complex obtained in Comparative Examples 1 to 3 was crushed to a fine powder with a mortar, and the powder was manufactured by filling in a powder cell (PSH-002, manufactured by JASCO Corporation) under a dry air atmosphere.

  The measurement results of the emission spectrum (excitation light: 380 nm) of the europium complex (1) obtained in Examples 1 to 9 are shown in FIGS. 2 to 8, and optical containing the europium complex (1) of the present invention obtained in Example 10 The measurement result of the emission spectrum (excitation light 340 nm) of the material is shown in FIG. 11, and the measurement result of the emission spectrum (excitation light 320 nm) of the optical material containing the europium complex (1) of the present invention obtained in Example 11 is shown. It is shown in 12. Emissions of about 593 nm, 612 nm, 653 nm and 699 nm based on the ff electronic transitions characteristic of the Eu (III) complex were observed.

  The evaluation results of the emission quantum yield at an excitation light wavelength of 380 nm of the europium complex (1) obtained in Examples 1 to 9 are shown in Table 1.

The light resistance was evaluated by the method shown below. The light resistance evaluation of Examples 1 to 9 and Comparative Examples 1 to 3 was performed by measuring the emission intensity at the maximum emission wavelength around 615 nm with a spectrophotometer (FP-6500, manufactured by JASCO Corporation). The measurement conditions were: excitation side slit 5 nm, fluorescence side slit 5 nm, and excitation light wavelength 380 nm. Then, using a UV light irradiator (manufactured by Ushio Inc., SP-9) and a lens, UV light of 200 mW / cm ² (365 nm) was applied for a predetermined time (0 to 24 hours) at room temperature. The luminescence intensity of the sample after UV light irradiation is measured again by a spectrophotometer, the luminescence intensity residual rate from the initial state is calculated by the following equation, the UV light irradiation time is taken with the X axis as the luminescence intensity residual rate and Y axis The sex was evaluated.

Remaining ratio of luminescence intensity (%) (I / I ₀ ) = (emission intensity at maximum emission wavelength after UV light irradiation) / (emission intensity at maximum emission wavelength before UV irradiation) × 100
The evaluation results of light resistance of the europium complexes obtained in Comparative Examples 1 to 3 are shown in FIG. 13, and the evaluation results of light resistance of the europium complexes (1) of the present invention obtained in Examples 1 to 9 are shown in FIGS. As a result, the results of the residual luminescence intensity ratio 24 hours after UV light irradiation are shown in Table 2.

  As shown in FIGS. 14-22, the europium complex (1) of the present invention characterized by having a specific substituent at the ortho position of the phenyl group on the phosphorus atom of phosphine oxide is emitted by UV light and its luminescence intensity It was found that it was difficult to lower and had excellent light resistance.

  On the other hand, in the compounds specifically described in RUB1453869 and JP-A-2003-81986 (Comparative Example 1), the decrease in emission intensity is large, and the meta position of the phenyl group on the phosphorus atom of phosphine oxide (Comparative Example 2) The compound having a specific substituent at the) and para positions (comparative example 3) also has a large decrease in emission intensity.

  The europium complex (1) of the present invention has high photostability as compared with the europium complex having triphenylphosphine oxide, even if it is irradiated with light for a long time, the emission intensity is not attenuated. In addition, the europium complex (1) of the present invention has high solubility, is easy to dissolve in organic solvents, polymer materials and the like, and can be uniformly dispersed. Therefore, it is useful as light emitting materials and wavelength conversion materials, such as a film for photovoltaics, an agricultural film, an LED phosphor, and a security ink.

Claims (7)

General formula (1)
{Wherein, Z ¹ , Z ² and Z ³ are each independently 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, carbon Groups of 1 to 3 fluoroalkyloxy group, a naphthyl group which may be substituted with a fluorine atom, a pyridyl group which may be substituted with a fluorine atom, or a group represented by the general formula (2)
[Wherein, R ¹ , R ³ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl having 1 to 3 carbon atoms A group, a fluoroalkyloxy group having 1 to 3 carbon atoms, a phenyl group which may be substituted with a fluorine atom, a hydroxyl group or a cyano group. Each of R ² and R ⁴ independently represents a hydrogen atom or a fluorine atom. Represents]. However, Z ¹ , Z ² and Z ³ can not simultaneously be hydrogen atoms. Each of W ¹ and W ² independently represents an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, phenyl, 2-thienyl group or 3-thienyl group. } The europium complex shown by}. The europium complex according to claim ^1, wherein W ¹ and W ² are each independently a fluoroalkyl group having 1 to 6 carbon atoms. Each of Z ¹ , Z ² and Z ³ independently represents a hydrogen atom, a methyl group, a methyloxy group, or a group represented by the general formula (2) [in the general formula (2), R ¹ , R ³ and R ⁵ are Each independently, a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkyloxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkyloxy group having 1 to 3 carbon atoms or R ² and R ⁴ are hydrogen atoms. The europium complex according to claim 1 or 2, which is Formula (1) is represented by the following formulas 1-1 to 1-7, 1-22, and 1-23.
The europium complex according to any one of claims 1 to 3, which is one compound selected from the group consisting of An optical material comprising the europium complex according to any one of claims 1 to 4. The optical material according to claim 5, comprising the europium complex according to any one of claims 1 to 4 and a resin material. A wavelength conversion material using the optical material according to claim 5 or 6.