JP7023551B1 - Complex compounds, inks and resin compositions - Google Patents
Complex compounds, inks and resin compositions Download PDFInfo
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- JP7023551B1 JP7023551B1 JP2021068103A JP2021068103A JP7023551B1 JP 7023551 B1 JP7023551 B1 JP 7023551B1 JP 2021068103 A JP2021068103 A JP 2021068103A JP 2021068103 A JP2021068103 A JP 2021068103A JP 7023551 B1 JP7023551 B1 JP 7023551B1
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- 150000001875 compounds Chemical class 0.000 title abstract description 276
- 239000011342 resin composition Substances 0.000 title abstract description 14
- 239000000976 ink Substances 0.000 title description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 12
- 239000003446 ligand Substances 0.000 abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 43
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 238000000295 emission spectrum Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000006862 quantum yield reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 8
- -1 europium (III) ions Chemical class 0.000 description 8
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000004685 tetrahydrates Chemical class 0.000 description 7
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- ZUNOXMJBNMKYOM-UHFFFAOYSA-N 2-hydroxy-3-(trifluoromethyl)benzaldehyde Chemical compound OC1=C(C=O)C=CC=C1C(F)(F)F ZUNOXMJBNMKYOM-UHFFFAOYSA-N 0.000 description 4
- BXQPCQLNANMZFL-UHFFFAOYSA-N 2-hydroxy-5-(trifluoromethyl)benzaldehyde Chemical compound OC1=CC=C(C(F)(F)F)C=C1C=O BXQPCQLNANMZFL-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YHYNJGHMBMXAFB-UHFFFAOYSA-N 2-hydroxy-4-(trifluoromethyl)benzaldehyde Chemical compound OC1=CC(C(F)(F)F)=CC=C1C=O YHYNJGHMBMXAFB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- PONXTPCRRASWKW-ZIAGYGMSSA-N (1r,2r)-1,2-diphenylethane-1,2-diamine Chemical compound C1([C@@H](N)[C@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-ZIAGYGMSSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PONXTPCRRASWKW-UHFFFAOYSA-N NC(C(c1ccccc1)N)c1ccccc1 Chemical compound NC(C(c1ccccc1)N)c1ccccc1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 2
- XIEIIBATYNPUGR-ZZULHHKVSA-N Oc1cc(C(F)(F)F)ccc1/C=N/CC/N=C/c(ccc(C(F)(F)F)c1)c1O Chemical compound Oc1cc(C(F)(F)F)ccc1/C=N/CC/N=C/c(ccc(C(F)(F)F)c1)c1O XIEIIBATYNPUGR-ZZULHHKVSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011000 absolute method Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- PONXTPCRRASWKW-KBPBESRZSA-N diphenylethylenediamine Chemical compound C1([C@H](N)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-KBPBESRZSA-N 0.000 description 2
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000012982 x-ray structure analysis Methods 0.000 description 2
- GHWVXCQZPNWFRO-QWWZWVQMSA-N (2r,3r)-butane-2,3-diamine Chemical compound C[C@@H](N)[C@@H](C)N GHWVXCQZPNWFRO-QWWZWVQMSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- FABVMBDCVAJXMB-UHFFFAOYSA-N 3,5-dichloro-2-hydroxybenzaldehyde Chemical compound OC1=C(Cl)C=C(Cl)C=C1C=O FABVMBDCVAJXMB-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(CC*=C)[C@@](C(C)N(C)C=CC(C)=C)C=NCC Chemical compound CCC(CC*=C)[C@@](C(C)N(C)C=CC(C)=C)C=NCC 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- OVHWMFJGVITYRF-KVJLFNRQSA-N Oc(c(/C=N/CC/N=C/c(cc(cc1Cl)Cl)c1O)cc(Cl)c1)c1Cl Chemical compound Oc(c(/C=N/CC/N=C/c(cc(cc1Cl)Cl)c1O)cc(Cl)c1)c1Cl OVHWMFJGVITYRF-KVJLFNRQSA-N 0.000 description 1
- XOUSMQMTFCXZAG-PBUAHAPGSA-N Oc1c(/C=N/C(C(c2ccccc2)/N=C/c2cc(C(F)(F)F)ccc2O)c2ccccc2)cc(C(F)(F)F)cc1 Chemical compound Oc1c(/C=N/C(C(c2ccccc2)/N=C/c2cc(C(F)(F)F)ccc2O)c2ccccc2)cc(C(F)(F)F)cc1 XOUSMQMTFCXZAG-PBUAHAPGSA-N 0.000 description 1
- ZTPRTSARHVNYKP-PBUAHAPGSA-N Oc1c(/C=N/C(C(c2ccccc2)/N=C/c2cccc(C(F)(F)F)c2O)c2ccccc2)cccc1C(F)(F)F Chemical compound Oc1c(/C=N/C(C(c2ccccc2)/N=C/c2cccc(C(F)(F)F)c2O)c2ccccc2)cccc1C(F)(F)F ZTPRTSARHVNYKP-PBUAHAPGSA-N 0.000 description 1
- AMUUELMOLFMYOC-ZZULHHKVSA-N Oc1c(/C=N/CC/N=C/c2cccc(C(F)(F)F)c2O)cccc1C(F)(F)F Chemical compound Oc1c(/C=N/CC/N=C/c2cccc(C(F)(F)F)c2O)cccc1C(F)(F)F AMUUELMOLFMYOC-ZZULHHKVSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- SPALIFXDWQTXKS-UHFFFAOYSA-M tetrapentylazanium;bromide Chemical compound [Br-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SPALIFXDWQTXKS-UHFFFAOYSA-M 0.000 description 1
- SXAWRMKQZKPHNJ-UHFFFAOYSA-M tetrapentylazanium;chloride Chemical compound [Cl-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SXAWRMKQZKPHNJ-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
【課題】発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物の提供。
【解決手段】下記一般式（１）で表される、錯体化合物。
Ｘ＋［Ｅｕ（Ｌ１）（Ｌ２）］－ ・・・（１）
式（１）中、Ｌ１及びＬ２は各々独立に、下記一般式（２）で表される化合物から誘導される、Ｅｕ錯体の配位子であり、Ｘ＋は対カチオンである。
［化１］
【選択図】なし
PROBLEM TO BE SOLVED: To provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound.
SOLUTION: A complex compound represented by the following general formula (1).
X + [Eu (L 1 ) (L 2 ) ] -... (1)
In the formula (1), L 1 and L 2 are each independently derived from the compound represented by the following general formula (2), and are the ligands of the Eu complex, and X + is a counter cation.
[Chemical 1]
[Selection diagram] None
Description
本発明は、錯体化合物、インク及び樹脂組成物に関する。 The present invention relates to complex compounds, inks and resin compositions.
ユウロピウム（III）イオンを含む化合物には、紫外線を照射すると強い赤色発光を示すものがあり、インビジブルインク、発光標識試薬、有機ＥＬ素子、太陽電池の波長変換材料、白色ＬＥＤ等の発光材料として使用されている。
ユウロピウムを用いた高い発光強度を示す発光材料として、例えばＣｌを置換基として有するｓａｌｅｎ型シッフ塩基であるＮ，Ｎ’－ビス－３，５－ジクロロサリチリデンエチレンジアミン（Ｈ２（３，５－Ｃｌｓａｌｅｎ））を配位子とするユウロピウム（III）単核錯体が提案されている（例えば非特許文献１、２）。
Some compounds containing europium (III) ions emit strong red light when irradiated with ultraviolet rays, and are used as light emitting materials for invisible inks, light emitting labeling reagents, organic EL devices, wavelength conversion materials for solar cells, white LEDs, etc. Has been done.
As a light emitting material using europium that exhibits high light emission intensity, for example, N, N'-bis-3,5-dichlorosalicylideneethylenediamine (H 2 (3,5-), which is a salen-type Schiff base having Cl as a substituent, is used. A europium (III) mononuclear complex having Clsalen)) as a ligand has been proposed (for example,
しかし、非特許文献１、２に記載の単核錯体には未だ改善の余地があり、さらなる発光強度の向上が求められる。
本発明は、発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物を提供することを目的とする。
However, the mononuclear complexes described in
An object of the present invention is to provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound.
本発明は、下記の態様を有する。
［１］ 下記一般式（１）で表される、錯体化合物。
Ｘ＋［Ｅｕ（Ｌ１）（Ｌ２）］－ ・・・（１）
式（１）中、Ｌ１及びＬ２は各々独立に、下記一般式（２）で表される化合物から誘導される、Ｅｕ錯体の配位子であり、Ｘ＋は対カチオンである。
The present invention has the following aspects.
[1] A complex compound represented by the following general formula (1).
X + [Eu (L 1 ) (L 2 ) ] -... (1)
In the formula (1), L 1 and L 2 are each independently derived from the compound represented by the following general formula (2), and are the ligands of the Eu complex, and X + is a counter cation.
式（２）中、Ｒ１及びＲ２は各々独立に、水素原子、メチル基、フェニル基である。 In formula (2), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.
［２］ 前記［１］の錯体化合物を含む、インク。
［３］ 前記［１］の錯体化合物を含む、樹脂組成物。
[2] An ink containing the complex compound of the above [1].
[3] A resin composition containing the complex compound of the above [1].
本発明によれば、発光強度が高い錯体化合物と、これを含むインク及び樹脂組成物を提供できる。 According to the present invention, it is possible to provide a complex compound having high emission intensity, and an ink and a resin composition containing the complex compound.
以下、本発明を詳細に説明する。
ただし、以下に説明する実施の形態は、発明の趣旨をより良く理解させるため具体的に説明するものであり、特に指定のない限り発明内容を限定するものではなく、本発明の趣旨を逸脱しない範囲で種々の変更が可能である。
Hereinafter, the present invention will be described in detail.
However, the embodiments described below are specifically described in order to better understand the gist of the invention, and do not limit the content of the invention unless otherwise specified, and do not deviate from the gist of the present invention. Various changes are possible within the range.
［錯体化合物］
本発明の錯体化合物は、下記一般式（１）で表されるユウロピウム（III）単核錯体である。
Ｘ＋［Ｅｕ（Ｌ１）（Ｌ２）］－ ・・・（１）
式（１）中、Ｌ１及びＬ２は各々独立に、下記一般式（２）で表される化合物から誘導される、Ｅｕ錯体の配位子であり、Ｘ＋は対カチオンである。
対カチオンとしては、例えば（ＣｎＨ２ｎ＋１）４Ｎ＋、（ＣｍＨ２ｍ＋１）３ＮＨ＋、ＰＰｈ４
＋、アルカリ金属イオン（例えばＮａ＋、Ｋ＋等）、アルカリ金属の錯イオン（例えばクラウンエーテル錯体等）、銀イオン（Ａｇ＋）、銀の錯イオン（例えば［Ａｇ（ＰＰｈ３）４］＋等）などが挙げられる。なお、ｎは１～５の整数であり、ｍは１～５の整数であり、Ｐｈはフェニル基である。
[Complex compound]
The complex compound of the present invention is a europium (III) mononuclear complex represented by the following general formula (1).
X + [Eu (L 1 ) (L 2 ) ] -... (1)
In the formula (1), L 1 and L 2 are each independently derived from the compound represented by the following general formula (2), and are the ligands of the Eu complex, and X + is a counter cation.
Examples of the counter cation include (C n H 2n + 1 ) 4 N + , (C m H 2m + 1 ) 3 NH + , PPh 4 + , alkali metal ions (for example, Na + , K + , etc.), and alkali metal complex ions (for example). Crown ether complexes, etc.), silver ions (Ag + ), silver complex ions (eg, [Ag (PPh 3 ) 4 ] + , etc.) and the like. Note that n is an integer of 1 to 5, m is an integer of 1 to 5, and Ph is a phenyl group.
式（２）中、Ｒ１及びＲ２は各々独立に、水素原子、メチル基、フェニル基である。
Ｒ１及びＲ２としては各々独立に、発光強度がより高まる観点から水素原子、フェニル基が好ましく、Ｒ１及びＲ２の両方が水素原子であるか、フェニル基であることが好ましい。
式（２）中のトリフルオロメチル基（ＣＦ３）の位置は、３位でもよいし、４位でもよいし、５位でもよいが、錯体化合物の安定性及び透明性が高まり、インビジブルインクの材料として好適に用いられる観点から、３位又は５位が好ましい。すなわち、前記一般式（２）で表される化合物としては、下記一般式（２１）で表される化合物又は下記一般式（２２）で表される化合物が好ましい。
In formula (2), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.
As R 1 and R 2 , hydrogen atoms and phenyl groups are preferable from the viewpoint of further increasing the emission intensity, and it is preferable that both R 1 and R 2 are hydrogen atoms or phenyl groups.
The position of the trifluoromethyl group (CF 3 ) in the formula (2) may be the 3-position, the 4-position, or the 5-position, but the stability and transparency of the complex compound are enhanced, and the invisible ink is used. From the viewpoint of being preferably used as a material, the 3-position or 5-position is preferable. That is, as the compound represented by the general formula (2), the compound represented by the following general formula (21) or the compound represented by the following general formula (22) is preferable.
式（２１）及び式（２２）中、Ｒ１及びＲ２は各々独立に、水素原子、メチル基、フェニル基である。 In formulas (21) and (22), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.
なお、本発明において、前記一般式（２）で表される化合物を「化合物（２）」又は「トリフルオロメチル基を有するｓａｌｅｎ型シッフ塩基」ともいう。特に、式（２）中のＲ１及びＲ２が水素原子である場合において、トリフルオロメチル基を３位の位置に有する化合物を「Ｈ２（３－ＣＦ３ｓａｌｅｎ）」と略し、トリフルオロメチル基を４位の位置に有する化合物を「Ｈ２（４－ＣＦ３ｓａｌｅｎ）」と略し、トリフルオロメチル基を５位の位置に有する化合物を「Ｈ２（５－ＣＦ３ｓａｌｅｎ）」と略す。また、Ｒ１及びＲ２がフェニル基である場合において、トリフルオロメチル基を３位の位置に有する化合物を「Ｈ２（３－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）」又は「Ｈ２（３－ＣＦ３ｓａｌ－（Ｓ，Ｓ）－ｓｔｉｅｎ）」と略し、トリフルオロメチル基を４位の位置に有する化合物を「Ｈ２（４－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）」又は「Ｈ２（４－ＣＦ３ｓａｌ－（Ｓ，Ｓ）－ｓｔｉｅｎ）」と略し、トリフルオロメチル基を５位の位置に有する化合物を「Ｈ２（５－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）」又は「Ｈ２（５－ＣＦ３ｓａｌ－（Ｓ，Ｓ）－ｓｔｉｅｎ）」と略す。
また、本発明において、前記一般式（２１）で表される化合物を「化合物（２１）」ともいい、前記一般式（２２）で表される化合物を「化合物（２２）」ともいう。化合物（２１）は、トリフルオロメチル基を３位の位置に有する化合物であり、化合物（２２）は、トリフルオロメチル基を５位の位置に有する化合物である。
In the present invention, the compound represented by the general formula (2) is also referred to as "compound (2)" or "salen-type Schiff base having a trifluoromethyl group". In particular, when R 1 and R 2 in the formula (2) are hydrogen atoms, the compound having a trifluoromethyl group at the 3-position position is abbreviated as "H 2 (3-CF 3 salon)" and is trifluoro. The compound having a methyl group at the 4-position position is abbreviated as "H 2 (4-CF 3 salon)", and the compound having a trifluoromethyl group at the 5-position position is referred to as "H 2 (5-CF 3 salon)". Abbreviate. Further, when R 1 and R 2 are phenyl groups, the compound having a trifluoromethyl group at the 3-position position is "H 2 (3-CF 3 sal- (R, R) -sien)" or "H". 2 (3-CF 3 sal- (S, S) -steen) ”is abbreviated as“ H 2 (4-CF 3 sal- (R, R) -steen), which is a compound having a trifluoromethyl group at the 4-position position. ) ”Or“ H 2 (4-CF 3 sal- (S, S) -steen) ”, and the compound having a trifluoromethyl group at the 5-position position is“ H 2 (5-CF 3 sal- (R). , R) -steen) "or" H 2 (5-CF 3 sal- (S, S) -steen) ".
Further, in the present invention, the compound represented by the general formula (21) is also referred to as "compound (21)", and the compound represented by the general formula (22) is also referred to as "compound (22)". Compound (21) is a compound having a trifluoromethyl group at the 3-position position, and compound (22) is a compound having a trifluoromethyl group at the 5-position position.
化合物（２）は、式（２）中のＯとＮがＥｕに結合することで、下記一般式（１Ａ）で表されるように、Ｅｕに配位する。すなわち、本発明の錯体化合物は、下記一般式（１Ａ）で表される。 The compound (2) is coordinated to Eu as represented by the following general formula (1A) by binding O and N in the formula (2) to Eu. That is, the complex compound of the present invention is represented by the following general formula (1A).
式（１）中のＬ１は、式（１Ａ）中のＯ１１－Ａ１１－Ｎ１１－Ａ１２－Ｎ１２－Ａ１３－Ｏ１２（ただし、Ｏ１１とＯ１２とＮ１１とＮ１２のＥｕと結合する結合手は省略する。）に相当し、式（１）中のＬ２は、式（１Ａ）中のＯ２１－Ａ２１－Ｎ２１－Ａ２２－Ｎ２２－Ａ２３－Ｏ２２（ただし、Ｏ２１とＯ２２とＮ２１とＮ２２のＥｕと結合する結合手は省略する。）に相当する。
式（１Ａ）中のＯ１１－Ａ１１－Ｎ１１－Ａ１２－Ｎ１２－Ａ１３－Ｏ１２は下記一般式（２Ａ）であり、式（１Ａ）中のＯ２１－Ａ２１－Ｎ２１－Ａ２２－Ｎ２２－Ａ２３－Ｏ２２は下記一般式（２Ｂ）であり、式（１Ａ）中のＸ＋は対カチオンである。なお、下記一般式（２Ａ）において、Ｏ１１とＯ１２とＮ１１とＮ１２のＥｕと結合する結合手は省略する。また、下記一般式（２Ｂ）において、Ｏ２１とＯ２２とＮ２１とＮ２２のＥｕと結合する結合手は省略する。
L 1 in the formula (1) is O 11 -A 11 -N 11 -A 12 -N 12 -A 13 -O 12 in the formula (1A) (however, O 11 and O 12 and N 11 and N 12 ). The binding hand that binds to Eu is omitted.), And L 2 in the formula (1) is O 21 -A 21 -N 21 -A 22 -N 22 -A 23- in the formula (1A). It corresponds to O 22 (however, the coupling hand that binds to Eu of O 21 and O 22 and N 21 and N 22 is omitted).
O 11 -A 11 -N 11 -A 12 -N 12 -A 13 -O 12 in the formula (1A) is the following general formula (2A), and O 21 -A 21 -N 21 in the formula (1A). -A 22 -N 22 -A 23 -O 22 is the following general formula (2B), and X + in the formula (1A) is a counter cation. In the following general formula (2A), the bond that binds Eu of O 11 and O 12 and N 11 and N 12 is omitted. Further, in the following general formula (2B), the bond that binds Eu of O 21 and O 22 and N 21 and N 22 is omitted.
式（２Ａ）及び式（２Ｂ）中、Ｒ１及びＲ２は各々独立に、水素原子、メチル基、フェニル基である。 In formula (2 A ) and formula (2 B ), R 1 and R 2 are independently hydrogen atoms, methyl groups, and phenyl groups, respectively.
前記一般式（１）で表される錯体化合物は、例えば以下のようにして製造できる。すなわち、本実施形態の錯体化合物の製造方法は、以下に示す工程（ａ）及び工程（ｂ）を含む。
まず、溶媒中にて化合物（３）と化合物（４）とを反応させ、化合物（２）を得る（工程（ａ））。
The complex compound represented by the general formula (1) can be produced, for example, as follows. That is, the method for producing the complex compound of the present embodiment includes the following steps (a) and (b).
First, the compound (3) and the compound (4) are reacted in a solvent to obtain the compound (2) (step (a)).
化合物（３）としては、２－ヒドロキシ－３－トリフルオロメチルベンズアルデヒド、２－ヒドロキシ－４－トリフルオロメチルベンズアルデヒド、２－ヒドロキシ－５－トリフルオロメチルベンズアルデヒドが挙げられる。
化合物（４）としては、エチレンジアミン、（１Ｒ，２Ｒ）－１，２－ジフェニルエチレンジアミン、（１Ｓ，２Ｓ）－１，２－ジフェニルエチレンジアミン、（２Ｒ，３Ｒ）－２，３－ブタンジアミン、（２Ｓ，３Ｓ）－２，３－ブタンジアミンなどが挙げられる。
溶媒としては、メタノール、エタノール、プロパノール等のアルコール系溶媒などが挙げられる。
Examples of the compound (3) include 2-hydroxy-3-trifluoromethylbenzaldehyde, 2-hydroxy-4-trifluoromethylbenzaldehyde, and 2-hydroxy-5-trifluoromethylbenzaldehyde.
Examples of the compound (4) include ethylenediamine, (1R, 2R) -1,2-diphenylethylenediamine, (1S, 2S) -1,2-diphenylethylenediamine, (2R, 3R) -2,3-butanediamine, (2S). , 3S) -2,3-butanediamine and the like.
Examples of the solvent include alcoholic solvents such as methanol, ethanol and propanol.
化合物（３）と化合物（４）との反応割合、すなわち化合物（３）／化合物（４）で表されるモル比は、１．９５～３が好ましく、２～２．５がより好ましい。モル比が上記範囲内であれば、未反応の化合物（３）や化合物（４）の割合が少なく、化合物（２）を高収率で得ることができる。
工程（ａ）の反応温度は、２０～５０℃が好ましく、２５～４５℃がより好ましい。
工程（ａ）の反応時間は、０．５～３時間が好ましく、１～２時間がより好ましい。
The reaction ratio between the compound (3) and the compound (4), that is, the molar ratio represented by the compound (3) / the compound (4) is preferably 1.95 to 3, more preferably 2 to 2.5. When the molar ratio is within the above range, the ratio of the unreacted compound (3) and the compound (4) is small, and the compound (2) can be obtained in a high yield.
The reaction temperature in the step (a) is preferably 20 to 50 ° C, more preferably 25 to 45 ° C.
The reaction time of the step (a) is preferably 0.5 to 3 hours, more preferably 1 to 2 hours.
次いで、溶媒中にて化合物（２）と化合物（５）と化合物（６）とを反応させ、前記一般式（１）で表される錯体化合物（以下、「化合物（１）」ともいう。）を得る（工程（ｂ））。 Next, the compound (2), the compound (5), and the compound (6) are reacted in a solvent, and the complex compound represented by the general formula (1) (hereinafter, also referred to as “compound (1)”). (Step (b)).
化合物（５）は、ユウロピウム（III）を含む化合物である。化合物（５）としては、例えば酢酸ユウロピウム（III）ｎ水和物、ユウロピウム（III）アセチルアセトナート二水和物などが挙げられる。
化合物（６）は、式（１）中のＸ＋（対カチオン）の由来となる化合物である。化合物（６）としては、例えばテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド；テトラメチルアンモニウムブロミド、テトラエチルアンモニウムブロミド、テトラプロピルアンモニウムブロミド、テトラブチルアンモニウムブロミド、テトラペンチルアンモニウムブロミド等のテトラアルキルアンモニウムブロミド；テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、テトラプロピルアンモニウムクロリド、テトラブチルアンモニウムクロリド、テトラペンチルアンモニウムクロリド等のテトラアルキルアンモニウムクロリド；テトラフェニルホスホニウムブロミド；テトラフェニルホスホニウムクロリド；テトラエチルホスホニウムブロミド；テトラブチルホスホニウムクロリド；トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン等のトリアルキルアミン；水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等の水酸化アルカリ金属などが挙げられる。
なお、化合物（６）としてテトラアルキルアンモニウムブロミド、テトラアルキルアンモニウムクロリド、テトラフェニルホスホニウムブロミド、テトラフェニルホスホニウムクロリド、テトラエチルホスホニウムブロミド、テトラブチルホスホニウムクロリドなどを用いる場合には、化合物（２）のフェノール性水酸基のプロトンを引き抜くために、化合物（２）に対してモル比が１～３倍程度のピリジンやトリエチルアミンなどの塩基を加える。
溶媒としては、メタノール、エタノール、プロパノール等のアルコール系溶媒；アセトニトリル等のニトリル系溶媒などが挙げられる。
Compound (5) is a compound containing europium (III). Examples of the compound (5) include europium acetate (III) n hydrate, europium (III) acetylacetonate dihydrate and the like.
Compound (6) is a compound from which X + (anti-cation) in the formula (1) is derived. Examples of the compound (6) include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; tetramethylammonium bromide, tetraethylammonium bromide, and tetrapropylammonium. Tetraalkylammonium bromide such as bromide, tetrabutylammonium bromide, tetrapentylammonium bromide; tetraalkylammonium chloride such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride; tetraphenyl. Phosphonium bromide; Tetraphenylphosphonium chloride; Tetraethylphosphonium bromide; Tetrabutylphosphonium chloride; Trialkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine; lithium hydroxide, sodium hydroxide, potassium hydroxide, water Examples thereof include alkali metal hydroxides such as rubidium oxide and cesium hydroxide.
When tetraalkylammonium bromide, tetraalkylammonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride and the like are used as the compound (6), the phenolic hydroxyl group of the compound (2). In order to extract the protons of compound (2), a base such as pyridine or triethylamine having a molar ratio of about 1 to 3 times that of compound (2) is added.
Examples of the solvent include alcohol solvents such as methanol, ethanol and propanol; and nitrile solvents such as acetonitrile.
化合物（２）と化合物（５）との反応割合、すなわち化合物（２）／化合物（５）で表されるモル比は、１．９５～３が好ましく、２～２．２がより好ましい。モル比が上記範囲内であれば、未反応の化合物（２）や化合物（５）の割合が少なく、化合物（１）を高収率で得ることができる。
化合物（２）と化合物（６）との反応割合、すなわち化合物（２）／化合物（６）で表されるモル比は、０．５～２．０が好ましく、１．０～２．０がより好ましい。モル比が上記範囲内であれば、未反応の化合物（２）や化合物（６）の割合が少なく、化合物（１）を高収率で得ることができる。
工程（ｂ）では、予め化合物（２）と化合物（５）と溶媒に溶解、もしくは懸濁させて混合溶液を調製しておき、得られた混合溶液と化合物（６）とを混合することが好ましい。
工程（ｂ）の反応温度は、２０～５０℃が好ましく、２５～４５℃がより好ましい。
工程（ｂ）の反応時間は、０．５～３時間が好ましく、１～２時間がより好ましい。
The reaction ratio between the compound (2) and the compound (5), that is, the molar ratio represented by the compound (2) / the compound (5) is preferably 1.95 to 3, more preferably 2 to 2.2. When the molar ratio is within the above range, the ratio of the unreacted compound (2) and the compound (5) is small, and the compound (1) can be obtained in a high yield.
The reaction ratio between the compound (2) and the compound (6), that is, the molar ratio represented by the compound (2) / the compound (6) is preferably 0.5 to 2.0, preferably 1.0 to 2.0. More preferred. When the molar ratio is within the above range, the ratio of the unreacted compound (2) and the compound (6) is small, and the compound (1) can be obtained in a high yield.
In the step (b), a mixed solution may be prepared by dissolving or suspending the compound (2) and the compound (5) in a solvent in advance, and the obtained mixed solution and the compound (6) may be mixed. preferable.
The reaction temperature in the step (b) is preferably 20 to 50 ° C, more preferably 25 to 45 ° C.
The reaction time of the step (b) is preferably 0.5 to 3 hours, more preferably 1 to 2 hours.
以上説明した本発明の錯体化合物は、ユウロピウム（III）に、上述した特定の配位子、すなわちトリフルオロメチル基を有するｓａｌｅｎ型シッフ塩基が配位しているため、発光強度が高い。具体的には、固体の状態及び液体の状態で、３２０～３８０ｎｍの波長の光を照射すると強く発光する。
特に、トリフルオロメチル基の位置が３位又は５位である錯体化合物は、白色光の下では、固体の状態で白色であり、液体の状態で無色透明である（すなわち、色として認識できない）ことから、インビジブルインクの材料として好適に用いられる。
なお、トリフルオロメチル基の位置が４位である錯体化合物は、白色光の下では、固体の状態及び液体の状態で共に薄い黄色である。
The complex compound of the present invention described above has high emission intensity because the above-mentioned specific ligand, that is, a salen-type Schiff base having a trifluoromethyl group is coordinated with europium (III). Specifically, it emits strong light when irradiated with light having a wavelength of 320 to 380 nm in a solid state and a liquid state.
In particular, the complex compound in which the position of the trifluoromethyl group is at the 3-position or 5-position is white in the solid state and colorless and transparent in the liquid state (that is, it cannot be recognized as a color) under white light. Therefore, it is suitably used as a material for invisible ink.
The complex compound in which the position of the trifluoromethyl group is at the 4-position is pale yellow in both the solid state and the liquid state under white light.
本発明の錯体化合物は、インビジブルインク、発光標識試薬、有機ＥＬ素子、太陽電池の波長変換材料、白色ＬＥＤ等の発光材料として好適である。 The complex compound of the present invention is suitable as a light emitting material such as an invisible ink, a light emitting labeling reagent, an organic EL element, a wavelength conversion material for a solar cell, and a white LED.
［インク］
本発明のインクは、上述した本発明の錯体化合物と、溶媒とを含み、必要に応じてバインダ、任意成分を含んでいてもよい。
溶媒としては、例えばアセトニトリル等のニトリル系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；エチルアセテート、プロピルアセテート等のエステル系溶媒；ジクロロメタン、クロロホルム等のハロゲン化アルキル系溶媒などが挙げられる。
[ink]
The ink of the present invention contains the above-mentioned complex compound of the present invention and a solvent, and may contain a binder and an optional component, if necessary.
Examples of the solvent include a nitrile solvent such as acetonitrile; a ketone solvent such as acetone and methyl ethyl ketone; an ester solvent such as ethyl acetate and propyl acetate; and an alkyl halide solvent such as dichloromethane and chloroform.
バインダとしては、例えばポリアクリレート又はポリメタクリレート（例えばポリメチルメタクリレート）、ポリスチレン、ポリオレフィン（例えばポリエチレン）、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリールスルホン、ポリアリールエーテル、ポリビニル誘導体、セルロース誘導体、ポリウレタン、ポリアミド、ポリイミド、ポリエステル、シリコーン樹脂などが挙げられる。 As the binder, for example, polyacrylate or polymethacrylate (for example, polymethylmethacrylate), polystyrene, polyolefin (for example, polyethylene), polycarbonate, polysulfone, polyethersulfone, polyarylsulfone, polyarylether, polyvinyl derivative, cellulose derivative, polyurethane, polyamide. , Polyethylene, polyester, silicone resin and the like.
任意成分としては、例えば界面活性剤、保湿剤、ｐＨ調整剤、消泡剤、酸化防止剤、還元防止剤などが挙げられる。 Examples of the optional component include a surfactant, a moisturizer, a pH adjuster, an antifoaming agent, an antioxidant, an antioxidant and the like.
錯体化合物の含有量は、インクの総質量に対して０．１～２質量％が好ましく、０．５～１質量％がより好ましい。
溶媒の含有量は、インクの総質量に対して９８～９９．９質量％が好ましく、９９～９９．５質量％がより好ましい。
バインダの含有量は、インクの総質量に対して５質量％以下が好ましく、１質量％以下がより好ましい。
任意成分の含有量は、インクの総質量に対して５質量％以下が好ましく、１質量％以下がより好ましい。
なお、インクに含まれる全ての成分の含有量の合計が、１００質量％となるものとする。
The content of the complex compound is preferably 0.1 to 2% by mass, more preferably 0.5 to 1% by mass, based on the total mass of the ink.
The content of the solvent is preferably 98 to 99.9% by mass, more preferably 99 to 99.5% by mass, based on the total mass of the ink.
The binder content is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the ink.
The content of the optional component is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the ink.
It is assumed that the total content of all the components contained in the ink is 100% by mass.
本発明のインクは、上述した本発明の錯体化合物を含むので、白色光の下では無色透明又は薄い黄色であるが、３２０～３８０ｎｍの波長の光を照射すると強く発光する。
よって、本発明のインクは、インビジブルインクとして好適である。
Since the ink of the present invention contains the complex compound of the present invention described above, it is colorless and transparent or pale yellow under white light, but emits strong light when irradiated with light having a wavelength of 320 to 380 nm.
Therefore, the ink of the present invention is suitable as an invisible ink.
［樹脂組成物］
本発明の樹脂組成物は、上述した本発明の錯体化合物と、樹脂成分とを含み、必要に応じて任意成分を含んでいてもよい。
樹脂成分としては、ポリアミド、ポリエステル、ポリカーボネート、ポリエーテルスルホン、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリイミド、ポリテトラフルオロエチレン、ポリエーテル、ポリオレフィン、液晶ポリマー、ポリアリレート、ポリスルホン、ポリアクリロニトリルスチレン、ポリスチレン、ポリアクリロニトリル、ポリメチルメタクリレート（ＰＭＭＡ）、ポリグリシジルメタクリレート（ＰＧＭＡ）、アクリロニトリル－ブタジエン－スチレンコポリマー（ＡＢＳ）等の熱可塑性樹脂；エポキシ樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、マレイミド樹脂、フェノール樹脂等の熱硬化性樹脂などが挙げられる。
[Resin composition]
The resin composition of the present invention contains the above-mentioned complex compound of the present invention and a resin component, and may contain an arbitrary component if necessary.
Resin components include polyamide, polyester, polycarbonate, polyether sulfone, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, polysulfone, etc. Thermoplastic resins such as polyacrylonitrile styrene, polystyrene, polyacrylonitrile, polymethylmethacrylate (PMMA), polyglycidylmethacrylate (PGMA), acrylonitrile-butadiene-styrene copolymer (ABS); epoxy resin, vinyl ester resin, unsaturated polyester resin, Examples thereof include thermocurable resins such as polyimide resin, maleimide resin, and phenol resin.
任意成分としては、例えば難燃剤、滑剤、離型剤、安定化剤、強化剤、酸化防止剤、可塑剤、粘度調整剤、顔料などが挙げられる。 Examples of the optional component include flame retardants, lubricants, mold release agents, stabilizers, strengthening agents, antioxidants, plasticizers, viscosity modifiers, pigments and the like.
錯体化合物の含有量は、樹脂組成物の総質量に対して０．１～１質量％が好ましく、０．２～０．５質量％がより好ましい。
樹脂成分の含有量は、樹脂組成物の総質量に対して９９～９９．９質量％が好ましく、９９．５～９９．８質量％が好ましい。
任意成分の含有量は、樹脂組成物の総質量に対して５質量％以下が好ましく、１質量％以下がより好ましい。
なお、樹脂組成物に含まれる全ての成分の含有量の合計が、１００質量％となるものとする。
The content of the complex compound is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.5% by mass, based on the total mass of the resin composition.
The content of the resin component is preferably 99 to 99.9% by mass, preferably 99.5 to 99.8% by mass, based on the total mass of the resin composition.
The content of the optional component is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total mass of the resin composition.
It is assumed that the total content of all the components contained in the resin composition is 100% by mass.
本発明の樹脂組成物を成形することで成形体が得られる。
成形方法としては、例えば射出成形法、押出成形法、圧縮成形、ブロー成形法、カレンダー成形法などが挙げられる。
こうして得られた成形体は、例えば自動車分野、ＯＡ機器分野、家電、電気・電子分野、建築分野、生活・化粧品分野、医用品分野等の種々の材料として、工業的に広く利用することができる。
A molded product can be obtained by molding the resin composition of the present invention.
Examples of the molding method include an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, a calendar molding method and the like.
The molded product thus obtained can be widely used industrially as various materials in, for example, automobile fields, OA equipment fields, home appliances, electric / electronic fields, construction fields, daily life / cosmetics fields, medical supplies fields, and the like. ..
本発明の樹脂組成物、及びこれを成形した成形体は、上述した本発明の錯体化合物を含むので、白色光の下では無色透明又は薄い黄色であるが、３２０～３８０ｎｍの波長の光を照射すると強く発光する。 Since the resin composition of the present invention and the molded product obtained by molding the same contain the complex compound of the present invention described above, the resin composition is colorless and transparent or pale yellow under white light, but is irradiated with light having a wavelength of 320 to 380 nm. Then it emits a strong light.
以下、実施例を示して本発明を詳細に説明するが、本発明は以下の記載によって限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
［配位子の製造］
＜Ｈ２（３－ＣＦ３ｓａｌｅｎ）の合成＞
化合物（３－１）として２－ヒドロキシ－３－トリフルオロメチルベンズアルデヒド１．００ｇ（５．２９ｍｍｏｌ）を溶解したエタノール溶液２０ｍＬに、化合物（４－１）としてエチレンジアミン０．１６ｇ（２．６５ｍｍｏｌ）を加え、３０℃で１時間撹拌した。冷却後、生じた白色沈殿を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（２１－１）であるＨ２（３－ＣＦ３ｓａｌｅｎ）を収量０．９９ｇ、収率９２％で得た。
[Manufacturing of ligand]
<Synthesis of H 2 (3-CF 3 salon)>
To 20 mL of an ethanol solution in which 1.00 g (5.29 mmol) of 2-hydroxy-3-trifluoromethylbenzaldehyde was dissolved as compound (3-1), 0.16 g (2.65 mmol) of ethylenediamine as compound (4-1) was added. In addition, the mixture was stirred at 30 ° C. for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol and dried to give compound (21-1) H 2 (3-CF 3 salon) in a yield of 0.99 g and a yield of 92%. Obtained.
＜Ｈ２（４－ＣＦ３ｓａｌｅｎ）の合成＞
化合物（３－２）として２－ヒドロキシ－４－トリフルオロメチルベンズアルデヒド２．００ｇ（１０．６ｍｍｏｌ）を溶解したエタノール溶液２０ｍＬに、化合物（４－１）としてエチレンジアミン０．３２ｇ（５．３ｍｍｏｌ）を加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（２３－１）であるＨ２（４－ＣＦ３ｓａｌｅｎ）を収量１．８２ｇ、収率８４％で得た。
<Synthesis of H 2 (4-CF 3 salon)>
In 20 mL of an ethanol solution in which 2.00 g (10.6 mmol) of 2-hydroxy-4-trifluoromethylbenzaldehyde was dissolved as compound (3-2), 0.32 g (5.3 mmol) of ethylenediamine as compound (4-1) was added. In addition, the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol, dried, and the compound (23-1), H 2 (4-CF 3 salon), was yielded at a yield of 1.82 g and a yield of 84. Obtained in%.
＜Ｈ２（５－ＣＦ３ｓａｌｅｎ）の合成＞
化合物（３－３）として２－ヒドロキシ－５－トリフルオロメチルベンズアルデヒド３．８０ｇ（２０ｍｍｏｌ）を溶解したエタノール溶液５０ｍＬに、化合物（４－１）としてエチレンジアミン０．６０ｇ（１０ｍｍｏｌ）を加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（２２－１）であるＨ２（５－ＣＦ３ｓａｌｅｎ）を収量３．５５ｇ、収率８８％で得た。
<Synthesis of H 2 (5-CF 3 salon)>
To 50 mL of an ethanol solution in which 3.80 g (20 mmol) of 2-hydroxy-5-trifluoromethylbenzaldehyde was dissolved as compound (3-3), 0.60 g (10 mmol) of ethylenediamine as compound (4-1) was added, and the temperature was 40 ° C. Was stirred for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol, dried, and the compound (22-1), H 2 (5-CF 3 salon), was yielded at 3.55 g and 88. Obtained in%.
＜Ｈ２（３－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）の合成＞
化合物（３－１）として２－ヒドロキシ－３－トリフルオロメチルベンズアルデヒド１．００ｇ（５．２９ｍｍｏｌ）を溶解したエタノール溶液２０ｍＬに、化合物（４－２）として（１Ｒ，２Ｒ）－１，２－ジフェニルエチレンジアミン０．５６２ｇ（２．６５ｍｍｏｌ）を加え、４０℃で１時間撹拌した。冷却後、溶液を濃縮乾固し、水１００ｍＬを加えて撹拌した。生じた白色の沈殿物を濾過により回収し、水で洗い、乾燥させ、化合物（２１－２）であるＨ２（３－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）を収量１．４３ｇ、収率９７％で得た。
<Synthesis of H 2 (3-CF 3 sal- (R, R) -sien)>
(1R, 2R) -1,2- as compound (4-2) in 20 mL of ethanol solution in which 1.00 g (5.29 mmol) of 2-hydroxy-3-trifluoromethylbenzaldehyde was dissolved as compound (3-1). 0.562 g (2.65 mmol) of diphenylethylenediamine was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the solution was concentrated to dryness, 100 mL of water was added, and the mixture was stirred. The resulting white precipitate was collected by filtration, washed with water and dried to yield the compound (21-2) H 2 (3-CF 3 sal- (R, R) -sien) in a yield of 1.43 g. It was obtained with a yield of 97%.
＜Ｈ２（５－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）の合成＞
化合物（３－３）として２－ヒドロキシ－５－トリフルオロメチルベンズアルデヒド３．８０ｇ（２０ｍｍｏｌ）を溶解したエタノール溶液５０ｍＬに、化合物（４－２）として（１Ｒ，２Ｒ）－１，２－ジフェニルエチレンジアミン２．１２ｇ（１０ｍｍｏｌ）を加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（２２－２）であるＨ２（５－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）を収量４．６５ｇ、収率８４％で得た。
<Synthesis of H 2 (5-CF 3 sal- (R, R) -sien)>
(1R, 2R) -1,2-diphenylethylenediamine as compound (4-2) in 50 mL of ethanol solution in which 3.80 g (20 mmol) of 2-hydroxy-5-trifluoromethylbenzaldehyde was dissolved as compound (3-3). 2.12 g (10 mmol) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol and dried to give compound (22-2) H 2 (5-CF 3 sal- (R, R) -sien). It was obtained with a yield of 4.65 g and a yield of 84%.
＜Ｈ２（３，５－Ｃｌｓａｌｅｎ）の合成＞
化合物（３－４）として３，５－ジクロロ－２－ヒドロキシベンズアルデヒド３．８２ｇ（２０ｍｍｏｌ）を溶解したエタノール溶液５０ｍＬに、化合物（４－１）としてエチレンジアミン０．６０ｇ（１０ｍｍｏｌ）を加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（２４－１）であるＨ２（３，５－Ｃｌｓａｌｅｎ）を収量３．８６ｇ、収率９５％で得た。
<Synthesis of H 2 (3,5-Clsalen)>
To 50 mL of an ethanol solution in which 3.82 g (20 mmol) of 3,5-dichloro-2-hydroxybenzaldehyde as compound (3-4) was dissolved, 0.60 g (10 mmol) of ethylenediamine as compound (4-1) was added, and the temperature was 40 ° C. Was stirred for 1 hour. After cooling, the resulting white precipitate was collected by filtration, washed with a small amount of ethanol and dried to yield 3.86 g of compound (24-1) H 2 (3,5-Clsalen), 95 yields. Obtained in%.
［実施例１］
化合物（２１－１）であるＨ２（３－ＣＦ３ｓａｌｅｎ）０．４０４ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール３０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－１）としてテトラプロピルアンモニウムヒドロキシドの１０質量％水溶液１．０ｍＬ（０．５ｍｍｏｌ）加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（１－１）である錯体化合物（（Ｃ３Ｈ７）４Ｎ＋［Ｅｕ（３－ＣＦ３ｓａｌｅｎ）２］－）を収量０．５４０ｇ、収率９４％で得た。
なお、化合物（１－１）は、前記一般式（１Ａ）中のＸ＋が（Ｃ３Ｈ７）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が３位の位置である化合物に相当する。
化合物（１－１）は白色の粉末状であり、化合物（１－１）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－１）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 1]
0.404 g (1 mmol) of H 2 (3-CF 3 salon) which is compound (21-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 30 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 3 H 7 ) 4 N + [Eu (3-CF)) which is compound (1-1). 3 salen) 2 ] - ) was obtained with a yield of 0.540 g and a yield of 94%.
In the compound (1-1), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 3-position.
Compound (1-1) was in the form of a white powder, and the solution in which compound (1-1) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-1). The results are shown in Table 1.
［実施例２］
化合物（６－１）の代わりに化合物（６－２）としてテトラブチルアンモニウムヒドロキシドの１０質量％水溶液１．３ｍＬ（０．５ｍｍｏｌ）を用いた以外は、実施例１と同様にして化合物（１－２）である錯体化合物（（Ｃ４Ｈ９）４Ｎ＋［Ｅｕ（３－ＣＦ３ｓａｌｅｎ）２］－）を収量０．５６０ｇ、収率９３％で得た。
なお、化合物（１－２）は、前記一般式（１Ａ）中のＸ＋が（Ｃ４Ｈ９）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が３位の位置である化合物に相当する。
化合物（１－２）は白色の粉末状であり、化合物（１－２）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－２）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
また、化合物（１－２）の０．４０ｍｍ×０．３０ｍｍ×０．２０ｍｍの結晶について、単結晶Ｘ線構造解析を行った。Ｘ線回折強度の測定は、単結晶Ｘ線回折装置（Ｂｒｕｋｅｒ社製、製品名「Ｓｍａｒｔ ＡＰＥＸＩＩ ｕｌｔｒａ」）により、線源にＣｕ回転対陰極を用いて－１００℃で行った。初期構造はＳＨＥＬＸＳ－９７を用いて解き、構造の精密化はＳＨＥＬＸＬ－２０１３ソフトウエアパッケージを用いて行った。分子構造図を図１に示し、結晶データを以下に示す。
Ｃｒｙｓｔａｌ ｄａｔａ：Ｏｒｔｈｏｒｈｏｍｂｉｃ，Ｐｎａ２１，ａ＝２３．４０１３（７）Å，ｂ＝１０．４５０９（３）Å，ｃ＝４３．７７９８（１３）Å，Ｚ＝８，Ｒ＝０．０５４。
[Example 2]
Compound (1) was used in the same manner as in Example 1 except that 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide was used as compound (6-2) instead of compound (6-1). -2) The complex compound ((C 4 H 9 ) 4 N + [Eu (3-CF 3 salen) 2 ] - ) was obtained with a yield of 0.560 g and a yield of 93%.
In the compound (1-2), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 3-position.
Compound (1-2) was in the form of a white powder, and the solution in which compound (1-2) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-2). The results are shown in Table 1.
In addition, single crystal X-ray structure analysis was performed on the 0.40 mm × 0.30 mm × 0.20 mm crystals of compound (1-2). The X-ray diffraction intensity was measured by a single crystal X-ray diffractometer (manufactured by Bruker, product name "Smart APEXII ultra") at −100 ° C. using a Cu rotating anti-cathode as a radiation source. The initial structure was solved using SHELXS-97 and the refinement of the structure was performed using the SHELXL-2013 software package. The molecular structure diagram is shown in FIG. 1, and the crystal data is shown below.
Crystal data: Orthorhombic, Pna2 1 , a = 23.4013 (7) Å, b = 10.4059 (3) Å, c = 43.77798 (13) Å, Z = 8, R = 0.054.
［実施例３］
化合物（２３－１）であるＨ２（４－ＣＦ３ｓａｌｅｎ）０．４０４ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール３０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－１）としてテトラプロピルアンモニウムヒドロキシドの１０質量％水溶液１．０ｍＬ（０．５ｍｍｏｌ）加え、５０℃で１時間撹拌した。冷却後、混合溶液を濃縮乾固し、生じた固体を水に懸濁させた。沈殿を濾過により回収し、少量の１－プロパノールで洗い、乾燥させ、化合物（１－３）である錯体化合物（（Ｃ３Ｈ７）４Ｎ＋［Ｅｕ（４－ＣＦ３ｓａｌｅｎ）２］－）を収量０．３８４ｇ、収率６７％で得た。
なお、化合物（１－３）は、前記一般式（１Ａ）中のＸ＋が（Ｃ３Ｈ７）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が４位の位置である化合物に相当する。
化合物（１－３）は薄い黄色の粉末状であり、化合物（１－３）をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物（１－３）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 3]
0.404 g (1 mmol) of H 2 (4-CF 3 salon) which is compound (23-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 30 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, the mixed solution was concentrated to dryness and the resulting solid was suspended in water. The precipitate is collected by filtration, washed with a small amount of 1-propanol, dried and complex compound ((C 3 H 7 ) 4 N + [Eu (4-CF 3 salen) 2 ] -which is compound (1-3). ) Was obtained with a yield of 0.384 g and a yield of 67%.
In the compound (1-3), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 4-position.
Compound (1-3) was in the form of a pale yellow powder, and the solution in which compound (1-3) was dissolved in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-3). The results are shown in Table 1.
［実施例４］
化合物（６－１）の代わりに化合物（６－２）としてテトラブチルアンモニウムヒドロキシドの１０質量％水溶液１．３ｍＬ（０．５ｍｍｏｌ）を用いた以外は、実施例３と同様にして化合物（１－４）である錯体化合物（（Ｃ４Ｈ９）４Ｎ＋［Ｅｕ（４－ＣＦ３ｓａｌｅｎ）２］－）を収量０．４６８ｇ、収率７８％で得た。
なお、化合物（１－４）は、前記一般式（１Ａ）中のＸ＋が（Ｃ４Ｈ９）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が４位の位置である化合物に相当する。
化合物（１－４）は薄い黄色の粉末状であり、化合物（１－４）をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物（１－４）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 4]
Compound (1) was used in the same manner as in Example 3 except that 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide was used as compound (6-2) instead of compound (6-1). A complex compound ((C 4 H 9 ) 4 N + [Eu (4-CF 3 salen) 2 ] - ) which is -4) was obtained with a yield of 0.468 g and a yield of 78%.
In the compound (1-4), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 4-position.
Compound (1-4) was in the form of a pale yellow powder, and the solution in which compound (1-4) was dissolved in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-4). The results are shown in Table 1.
［実施例５］
化合物（２２－１）であるＨ２（５－ＣＦ３ｓａｌｅｎ）０．４０４ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール４０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－１）としてテトラプロピルアンモニウムヒドロキシドの１０質量％水溶液１．０ｍＬ（０．５ｍｍｏｌ）加え、４０℃で１時間撹拌した。冷却後、反応溶液を濃縮して乾固し、生じた白色の粉末を少量のエタノールで洗い、乾燥させ、化合物（１－５）である錯体化合物（（Ｃ３Ｈ７）４Ｎ＋［Ｅｕ（５－ＣＦ３ｓａｌｅｎ）２］－）を収量０．４４８ｇ、収率７８％で得た。
なお、化合物（１－５）は、前記一般式（１Ａ）中のＸ＋が（Ｃ３Ｈ７）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が５位の位置である化合物に相当する。
化合物（１－５）は白色の粉末状であり、化合物（１－５）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－５）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 5]
0.404 g (1 mmol) of H 2 (5-CF 3 salon) which is compound (22-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.0 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrapropylammonium hydroxide as compound (6-1) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the reaction solution is concentrated to dryness, the resulting white powder is washed with a small amount of ethanol, dried, and the complex compound ((C 3 H 7 ) 4 N + [Eu) which is compound (1-5). (5-CF 3 salen) 2 ] - ) was obtained with a yield of 0.448 g and a yield of 78%.
In the compound (1-5), X + in the general formula (1A) is (C 3 H 7 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 5-position.
Compound (1-5) was in the form of a white powder, and the solution in which compound (1-5) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-5). The results are shown in Table 1.
［実施例６］
化合物（２２－１）であるＨ２（５－ＣＦ３ｓａｌｅｎ）０．４０４ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール４０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－２）としてテトラブチルアンモニウムヒドロキシドの１０質量％水溶液１．３ｍＬ（０．５ｍｍｏｌ）加え、４０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（１－６）である錯体化合物（（Ｃ４Ｈ９）４Ｎ＋［Ｅｕ（５－ＣＦ３ｓａｌｅｎ）２］－）を収量０．５１８ｇ、収率８７％で得た。
なお、化合物（１－６）は、前記一般式（１Ａ）中のＸ＋が（Ｃ４Ｈ９）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基が５位の位置である化合物に相当する。
化合物（１－６）は白色の粉末状であり、化合物（１－６）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－６）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
また、化合物（１－６）の０．４５ｍｍ×０．２５ｍｍ×０．１０ｍｍの結晶について、単結晶Ｘ線構造解析を行った。Ｘ線回折強度の測定は、単結晶Ｘ線構造解析装置（株式会社リガク製、製品名「Ｒ－ＡＸＩＳ ＲＡＰＩＤ」）により、線源にＭｏ封入管を用いて２５℃で行った。初期構造はＳＨＥＬＸＳ－９７を用いて解き、構造の精密化はＳＨＥＬＸＬ－９７ソフトウエアパッケージを用いて行った。分子構造図を図２に示し、結晶データを以下に示す。
Ｃｒｙｓｔａｌ ｄａｔａ：Ｍｏｎｏｃｌｉｎｉｃ，Ｐ２１／ｃ，ａ＝１２．１６１１（３）Å，ｂ＝２１．０７８９（５）Å，ｃ＝２１．８８２６（５）Å，β＝９０．０１８（１）°，Ｚ＝４，Ｒ＝０．０５５。
[Example 6]
0.404 g (1 mmol) of H 2 (5-CF 3 salon) which is compound (22-1) and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.3 mL (0.5 mmol) of a 10 mass% aqueous solution of tetrabutylammonium hydroxide as compound (6-2) was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 4 H 9 ) 4 N + [Eu (5-CF)) which is compound (1-6). 3 salen) 2 ] - ) was obtained with a yield of 0.518 g and a yield of 87%.
In the compound (1-6), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds in which the trifluoromethyl group is at the 5-position.
Compound (1-6) was in the form of a white powder, and the solution in which compound (1-6) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-6). The results are shown in Table 1.
In addition, single crystal X-ray structure analysis was performed on 0.45 mm × 0.25 mm × 0.10 mm crystals of compound (1-6). The X-ray diffraction intensity was measured by a single crystal X-ray structure analyzer (manufactured by Rigaku Co., Ltd., product name "R-AXIS RAPID") at 25 ° C. using a Mo-encapsulated tube as a radiation source. The initial structure was solved using SHELXS-97 and the refinement of the structure was performed using the SHELXL-97 software package. The molecular structure diagram is shown in FIG. 2, and the crystal data is shown below.
Crystal data: Monoclinic, P2 1 / c, a = 12.1611 (3) Å, b = 21.0789 (5) Å, c = 21.8826 (5) Å, β = 90.188 (1) °, Z = 4, R = 0.055.
［実施例７］
化合物（２１－２）であるＨ２（３－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）０．５５５ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール５０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－３）としてテトラブチルアンモニウムブロミド０．９６０ｇ（３ｍｍｏｌ）と、化合物（６－４）としてトリエチルアミン０．５ｍＬを加え、５０℃で１時間撹拌した。冷却後、生じた白色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（１－７）である錯体化合物（（Ｃ４Ｈ９）４Ｎ＋［Ｅｕ（３－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）２］－）を収量０．６１４ｇ、収率８２％で得た。
なお、化合物（１－７）は、前記一般式（１Ａ）中のＸ＋が（Ｃ４Ｈ９）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２がフェニル基であり、トリフルオロメチル基が３位の位置である化合物に相当する。
化合物（１－７）は白色の粉末状であり、化合物（１－７）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－７）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 7]
Compound (21-2) H 2 (3-CF 3 sal- (R, R) -sien) 0.555 g (1 mmol) and Europium acetate (III) tetrahydrate 0 as compound (5-1) .201 g (0.5 mmol) was added to 50 mL of ethanol and stirred for 30 minutes to give a mixed solution. To the obtained mixed solution, 0.960 g (3 mmol) of tetrabutylammonium bromide as compound (6-3) and 0.5 mL of triethylamine as compound (6-4) were added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, the resulting white precipitate is collected by filtration, washed with a small amount of ethanol, dried and the complex compound ((C 4 H 9 ) 4 N + [Eu (3-CF)) which is compound (1-7). 3 sal- (R, R) -steen) 2 ] - ) was obtained with a yield of 0.614 g and a yield of 82%.
In the compound (1-7), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 correspond to the compound in which the phenyl group is located and the trifluoromethyl group is in the 3-position position.
Compound (1-7) was in the form of a white powder, and the solution in which compound (1-7) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-7). The results are shown in Table 1.
［実施例８］
化合物（２２－２）であるＨ２（５－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）０．５５５ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール５０ｍＬに加え、３０分撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－３）としてテトラブチルアンモニウムブロミド０．９６０ｇ（３ｍｍｏｌ）と、化合物（６－４）としてトリエチルアミン０．５ｍＬとを加え、５０℃で１時間撹拌した。冷却後、反応溶液を濃縮して乾固した後に水を加え、クリーム色の沈殿物を得た。沈殿物を濾過により回収し、水で洗い、乾燥させ、化合物（１－８）である錯体化合物（（Ｃ４Ｈ９）４Ｎ＋［Ｅｕ（５－ＣＦ３ｓａｌ－（Ｒ，Ｒ）－ｓｔｉｅｎ）２］－）を収量０．６６６ｇ、収率８８％で得た。
なお、化合物（１－８）は、前記一般式（１Ａ）中のＸ＋が（Ｃ４Ｈ９）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２がフェニル基であり、トリフルオロメチル基が５位の位置である化合物に相当する。
化合物（１－８）はクリーム色の粉末状であるが、化合物（１－８）をアセトニトリルに溶解させた溶液は無色透明であった。
化合物（１－８）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Example 8]
0.555 g (1 mmol) of H 2 (5-CF 3 sal- (R, R) -sien) which is compound (22-2) and europium (III)
In the compound (1-8), X + in the general formula (1A) is (C 4 H 9 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are phenyl groups, and the trifluoromethyl group is at the 5-position position, which corresponds to the compound.
Compound (1-8) was in the form of a cream-colored powder, but the solution in which compound (1-8) was dissolved in acetonitrile was colorless and transparent.
Elemental analysis was performed for each element of C, H, and N of compound (1-8). The results are shown in Table 1.
［比較例１］
化合物（２４－１）であるＨ２（３，５－Ｃｌｓａｌｅｎ）０．４０６ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をエタノール４０ｍＬに加え、1時間撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－４）としてトリエチルアミン１ｍＬを加え、６０℃で１時間撹拌した。冷却後、生じたクリーム色の沈殿物を濾過により回収し、少量のエタノールで洗い、乾燥させ、化合物（１－９）である錯体化合物（（Ｃ２Ｈ５）３ＮＨ＋［Ｅｕ（３，５－Ｃｌｓａｌｅｎ）２］－）を収率９４％で得た。
なお、化合物（１－９）は、前記一般式（１Ａ）中のＸ＋が（Ｃ２Ｈ５）３ＮＨ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基の代わりにＣｌを３位と５位の位置に有する化合物に相当する。
化合物（１－９）はクリーム色の粉末状であり、化合物（１－９）をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物（１－９）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Comparative Example 1]
0.406 g (1 mmol) of H 2 (3,5-Clsalen), which is compound (24-1), and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of ethanol and stirred for 1 hour to obtain a mixed solution. To the obtained mixed solution, 1 mL of triethylamine as compound (6-4) was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, the resulting cream-colored precipitate is collected by filtration, washed with a small amount of ethanol, dried, and the complex compound ((C 2 H 5 ) 3 NH + [Eu (3, 3)) which is compound (1-9). 5-Clsalen) 2 ] - ) was obtained in a yield of 94%.
In the compound (1-9), X + in the general formula (1A) is (C 2 H 5 ) 3 NH + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds having Cl at the 3rd and 5th positions instead of the trifluoromethyl group.
Compound (1-9) was in the form of a cream-colored powder, and the solution of compound (1-9) in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-9). The results are shown in Table 1.
［比較例２］
化合物（２４－１）であるＨ２（３，５－Ｃｌｓａｌｅｎ）０．４０６ｇ（１ｍｍｏｌ）と、化合物（５－１）として酢酸ユウロピウム（III）四水和物０．２０１ｇ（０．５ｍｍｏｌ）をメタノール４０ｍＬに加え、1時間撹拌し、混合溶液を得た。得られた混合溶液に、化合物（６－５）としてテトラエチルアンモニウムヒドロキシドの１０質量％水溶液０．７４ｍＬ（０．５ｍｍｏｌ）加え、６０℃で１時間撹拌した。冷却後、生じたクリーム色の沈殿物を濾過により回収し、少量のメタノールで洗い、乾燥させ、化合物（１－１０）である錯体化合物（（Ｃ２Ｈ５）４Ｎ＋［Ｅｕ（３，５－Ｃｌｓａｌｅｎ）２］－）を収率８１％で得た。
なお、化合物（１－１０）は、前記一般式（１Ａ）中のＸ＋が（Ｃ２Ｈ５）４Ｎ＋であり、前記一般式（２Ａ）及び前記一般式（２Ｂ）中のＲ１及びＲ２が水素原子であり、トリフルオロメチル基の代わりにＣｌを３位と５位の位置に有する化合物に相当する。
化合物（１－１０）はクリーム色の粉末状であり、化合物（１－１０）をアセトニトリルに溶解させた溶液は薄い黄色であった。
化合物（１－１０）のＣ、Ｈ、Ｎの各元素について元素分析を行った。結果を表１に示す。
[Comparative Example 2]
0.406 g (1 mmol) of H 2 (3,5-Clsalen), which is compound (24-1), and 0.201 g (0.5 mmol) of europium acetate (III) tetrahydrate as compound (5-1). The mixture was added to 40 mL of methanol and stirred for 1 hour to obtain a mixed solution. To the obtained mixed solution, 0.74 mL (0.5 mmol) of a 10 mass% aqueous solution of tetraethylammonium hydroxide as compound (6-5) was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, the resulting cream-colored precipitate is collected by filtration, washed with a small amount of methanol, dried, and the complex compound ((C 2 H 5 ) 4 N + [Eu (3, 3)) which is compound (1-10). 5-Clsalen) 2 ] - ) was obtained in a yield of 81%.
In the compound (1-10), X + in the general formula (1A) is (C 2 H 5 ) 4 N + , and R 1 in the general formula (2A) and the general formula (2B). And R 2 are hydrogen atoms and correspond to compounds having Cl at the 3rd and 5th positions instead of the trifluoromethyl group.
Compound (1-10) was in the form of a cream-colored powder, and the solution of compound (1-10) in acetonitrile was pale yellow.
Elemental analysis was performed for each element of C, H, and N of compound (1-10). The results are shown in Table 1.
［測定・評価］
＜吸収スペクトルの測定＞
実施例６で得られた錯体化合物（化合物（１－６））、及び比較例１で得られた錯体化合物（化合物（１－９））を、それぞれ濃度が２．０×１０－５ｍｏｌ／Ｌとなるようにアセトニトリルに溶解させた。得られた各アセトニトリル溶液について、分光光度計（日本分光株式会社製、製品名「Ｖ－５７０」）を用いて吸収スペクトルを測定した。結果を図３に示す。
また、実施例２で得られた錯体化合物（化合物（１－２））、及び実施例４で得られた錯体化合物（化合物（１－４））を濃度が２．０×１０－５ｍｏｌ／Ｌとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、分光光度計（日本分光株式会社製、製品名「Ｖ－５７０」）を用いて吸収スペクトルを測定した。結果を図４に示す。なお、図４には、実施例６で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルの結果も示す。
[Measurement / evaluation]
<Measurement of absorption spectrum>
The complex compound (compound (1-6)) obtained in Example 6 and the complex compound (compound (1-9)) obtained in Comparative Example 1 each had a concentration of 2.0 × 10-5 mol /. It was dissolved in acetonitrile so as to be L. The absorption spectrum of each of the obtained acetonitrile solutions was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V-570"). The results are shown in FIG.
Further, the complex compound (compound (1-2)) obtained in Example 2 and the complex compound (compound (1-4)) obtained in Example 4 had a concentration of 2.0 × 10-5 mol /. It was dissolved in acetonitrile so as to be L. The absorption spectrum of the obtained acetonitrile solution was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V-570"). The results are shown in FIG. In addition, FIG. 4 also shows the result of the absorption spectrum of the acetonitrile solution of the complex compound obtained in Example 6.
図３から明らかなように、実施例６で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルを測定したところ、３３７ｎｍに配位子のπ－π＊遷移に由来する吸収帯のピークがあることが分かった。その吸収帯の裾野は４００ｎｍ付近まで広がっているが、可視領域（４００～９００ｎｍ）にはかかっておらず、アセトニトリル溶液の色は無色透明であった。
一方、比較例１で得られた錯体化合物のアセトニトリル溶液の吸収スペクトルでは、３５９ｎｍに配位子のπ－π＊遷移に由来する吸収帯のピークがある。そして、その吸収帯の裾野は可視領域の４００ｎｍ以上の波長まで広がっており、アセトニトリル溶液の色は薄い黄色であった。
As is clear from FIG. 3, when the absorption spectrum of the acetonitrile solution of the complex compound obtained in Example 6 was measured, it was found that there was a peak in the absorption band derived from the π-π * transition of the ligand at 337 nm. Do you get it. The base of the absorption band extended to around 400 nm, but did not cover the visible region (400 to 900 nm), and the color of the acetonitrile solution was colorless and transparent.
On the other hand, in the absorption spectrum of the acetonitrile solution of the complex compound obtained in Comparative Example 1, there is a peak of the absorption band derived from the π-π * transition of the ligand at 359 nm. The base of the absorption band extended to a wavelength of 400 nm or more in the visible region, and the color of the acetonitrile solution was pale yellow.
また、図４から明らかなように、実施例２、４、６で得られた錯体化合物において、配位子のπ－π＊遷移に由来する吸収帯のピークは配位子のベンゼン環上にあるトリフルオロメチル基の位置によって異なることが分かった。すなわち、化合物（１－６）のπ－π＊吸収帯のピークが３３７ｎｍと最も短波長であり、化合物（１－４）のπ－π＊吸収帯のピークが３５２ｎｍと最も長波長であった。化合物（１－２）のπ－π＊吸収帯のピークは３４３ｎｍであり、化合物（１－６）及び化合物（１－４）の中間にあった。この吸収波長の違いは、電子吸引基であるトリフルオロメチル基の電子的影響によるものと考えられる。また、これらの化合物の固体粉末の色は、化合物（１－２）と化合物（１－６）が白色であり、化合物（１－４）が薄い黄色であり、吸収スペクトルの結果と一致している。 Further, as is clear from FIG. 4, in the complex compounds obtained in Examples 2, 4 and 6, the peak of the absorption band derived from the π-π * transition of the ligand is on the benzene ring of the ligand. It was found that it depends on the position of a certain trifluoromethyl group. That is, the peak of the π-π * absorption band of compound (1-6) was the shortest wavelength of 337 nm, and the peak of the π-π * absorption band of compound (1-4) was the longest wavelength of 352 nm. .. The peak of the π-π * absorption band of compound (1-2) was 343 nm, which was between compound (1-6) and compound (1-4). This difference in absorption wavelength is considered to be due to the electronic influence of the trifluoromethyl group, which is an electron-withdrawing group. In addition, the color of the solid powder of these compounds was white for compound (1-2) and compound (1-6) and light yellow for compound (1-4), which was consistent with the result of the absorption spectrum. There is.
＜発光特性の評価＞
（発光スペクトルの測定１）
実施例６で得られた錯体化合物を濃度が２．０×１０－６ｍｏｌ／Ｌとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、分光蛍光光度計（株式会社日立製作所製、製品名「Ｆ－７０００」）を用い、励起波長３３７ｎｍで溶液の発光スペクトルを測定した。結果を図５に示す。
<Evaluation of light emission characteristics>
(Measurement of emission spectrum 1)
The complex compound obtained in Example 6 was dissolved in acetonitrile so as to have a concentration of 2.0 × 10 -6 mol / L. With respect to the obtained acetonitrile solution, the emission spectrum of the solution was measured at an excitation wavelength of 337 nm using a spectrofluorometer (manufactured by Hitachi, Ltd., product name “F-7000”). The results are shown in FIG.
また、実施例６で得られた錯体化合物について、分光蛍光光度計（株式会社日立製作所製、製品名「Ｆ－７０００」）を用い、励起波長３３７ｎｍで固体の発光スペクトルを測定した。結果を図６に示す。 Further, for the complex compound obtained in Example 6, the emission spectrum of a solid was measured at an excitation wavelength of 337 nm using a spectrofluorometer (manufactured by Hitachi, Ltd., product name “F-7000”). The results are shown in FIG.
（発光スペクトルの測定２）
実施例２、４、６～８で得られた錯体化合物、及び比較例１、２で得られた錯体化合物を用い、キャスト法により以下のようにしてフィルムを作製した。
直径５．５ｃｍのアルミカップ中で錯体化合物０．００５ｍｍｏｌをジクロロメタン３０ｍＬに溶解させた後、撹拌しながらポリメチルメタクリレート（ＰＭＭＡ）１．００ｇを加えて溶解させ、混合溶液を得た。得られた混合溶液を３０℃で２４時間放置することでジクロロメタンを蒸発させて、厚さ０．３２±０．０２ｍｍのフィルムを得た。
得られたフィルムを縦８．８ｍｍ、横８．８ｍｍの大きさに切断し、積分球を搭載した分光蛍光光度計（株式会社日立製作所製、製品名「Ｆ－７０００」）を用い、励起波長３６５ｎｍで発光スペクトルを同一条件（同一の電圧、スリット幅）において測定した。
実施例６で得られた錯体化合物を含むフィルムの発光スペクトルを図７に示す。
実施例２、７で得られた錯体化合物、及び比較例１、２で得られた錯体化合物を含むフィルムの発光スペクトルを図８に示す。
実施例４、８で得られた錯体化合物、及び比較例１で得られた錯体化合物を含むフィルムの発光スペクトルを図９に示す。
(Measurement of emission spectrum 2)
Using the complex compounds obtained in Examples 2, 4, 6 to 8 and the complex compounds obtained in Comparative Examples 1 and 2, a film was prepared as follows by a casting method.
After dissolving 0.005 mmol of the complex compound in 30 mL of dichloromethane in an aluminum cup having a diameter of 5.5 cm, 1.00 g of polymethylmethacrylate (PMMA) was added and dissolved with stirring to obtain a mixed solution. Dichloromethane was evaporated by leaving the obtained mixed solution at 30 ° C. for 24 hours to obtain a film having a thickness of 0.32 ± 0.02 mm.
The obtained film was cut into a size of 8.8 mm in length and 8.8 mm in width, and an excitation wavelength was used using a spectral fluorometer (manufactured by Hitachi, Ltd., product name "F-7000") equipped with an integrating sphere. The emission spectrum was measured at 365 nm under the same conditions (same voltage, slit width).
The emission spectrum of the film containing the complex compound obtained in Example 6 is shown in FIG.
The emission spectrum of the film containing the complex compound obtained in Examples 2 and 7 and the complex compound obtained in Comparative Examples 1 and 2 is shown in FIG.
The emission spectra of the film containing the complex compound obtained in Examples 4 and 8 and the complex compound obtained in Comparative Example 1 are shown in FIG.
（量子収率の測定）
実施例２、４、６～８で得られた錯体化合物を、それぞれ濃度が２．０×１０－６ｍｏｌ／Ｌとなるように溶媒に溶解させた。得られた各溶液について、絶対ＰＬ量子収率測定装置（浜松ホトニクス株式会社製、製品名「Ｑｕａｎｔａｕｒｕｓ－ＱＹ Ｃ１１３４７－０１」）を用い、絶対法で溶液の量子収率を励起波長３６５ｎｍで測定した。結果を表２に示す。なお、溶媒としては、アセトニトリル、ＤＭＳＯ（ジメチルスルホキシド）、ＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）、アセトンのいずれかを用いた。結果を表２に示す。
(Measurement of quantum yield)
The complex compounds obtained in Examples 2, 4, 6 to 8 were dissolved in a solvent so as to have a concentration of 2.0 × 10-6 mol / L, respectively. For each of the obtained solutions, the quantum yield of the solution was measured at an excitation wavelength of 365 nm by an absolute method using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., product name "Quantaurus-QY C11347-01"). .. The results are shown in Table 2. As the solvent, any one of acetonitrile, DMSO (dimethyl sulfoxide), DMF (N, N-dimethylformamide), and acetone was used. The results are shown in Table 2.
一方、比較例１、２で得られた錯体化合物については、以下のようにして量子収率を測定した。
まず、比較例１で得られた錯体化合物を濃度が２．０×１０－６ｍｏｌ／Ｌとなるようにアセトニトリルに溶解させた。得られたアセトニトリル溶液について、積分球を搭載した分光蛍光光度計（株式会社日立製作所製、製品名「Ｆ－７０００」）を用い、絶対法で溶液の量子収率を励起波長３６５ｎｍで測定した。
次いで、比較例１で得られた錯体化合物を濃度が２．０×１０－６ｍｏｌ／ＬとなるようにＤＭＳＯ、ＤＭＦ、アセトンのいずれかの溶媒に溶解させた。得られた各溶液の量子収率を、比較例１のアセトニトリル溶液の量子収率の値（０．２４）を基準として、相対法により求めた。結果を表２に示す。
また、比較例２で得られた錯体化合物を濃度が２．０×１０－６ｍｏｌ／Ｌとなるようにアセトニトリル、ＤＭＳＯ、ＤＭＦ、アセトンのいずれかの溶媒に溶解させた。得られた各溶液の量子収率を、比較例１のアセトニトリル溶液の量子収率の値（０．２４）を基準として、相対法により求めた。結果を表２に示す。
On the other hand, for the complex compounds obtained in Comparative Examples 1 and 2, the quantum yields were measured as follows.
First, the complex compound obtained in Comparative Example 1 was dissolved in acetonitrile so as to have a concentration of 2.0 × 10 -6 mol / L. With respect to the obtained acetonitrile solution, the quantum yield of the solution was measured at an excitation wavelength of 365 nm by an absolute method using a spectrofluorometer equipped with an integrating sphere (manufactured by Hitachi, Ltd., product name “F-7000”).
Then, the complex compound obtained in Comparative Example 1 was dissolved in any solvent of DMSO, DMF, or acetone so as to have a concentration of 2.0 × 10 -6 mol / L. The quantum yield of each of the obtained solutions was determined by a relative method with reference to the quantum yield value (0.24) of the acetonitrile solution of Comparative Example 1. The results are shown in Table 2.
Further, the complex compound obtained in Comparative Example 2 was dissolved in any solvent of acetonitrile, DMSO, DMF or acetone so as to have a concentration of 2.0 × 10 -6 mol / L. The quantum yield of each of the obtained solutions was determined by a relative method with reference to the quantum yield value (0.24) of the acetonitrile solution of Comparative Example 1. The results are shown in Table 2.
実施例６で得られた錯体化合物（化合物（１－６））は、ブラックライト波長（３６５ｎｍ）付近の紫外線を照射すると、固体状及び溶液中のいずれにおいても赤色に発光した。図５は化合物（１－６）の溶液中での発光スペクトルであり、図６は化合物（１－６）の固体の発光スペクトルであり、図７は化合物（１－６）を含むフィルムの発光スペクトルである。これら図５～７から明らかなように、化合物（１－６）は６１４ｎｍに半値幅の狭いシャープな発光バンドを有する。
一方、比較例１で得られた錯体化合物（化合物（１－９））も、ブラックライト波長（３６５ｎｍ）付近の紫外線を照射すると、固体状及び溶液中のいずれにおいても赤色に発光した。また、化合物（１－９）の発光スペクトルも、化合物（１－６）の発光スペクトルと同様なスペクトルパターンを示す。
しかし、表２から明らかなように、化合物（１－６）と、化合物（１－９）の溶液の量子収率を比較したところ、化合物（１－６）の量子収率の値は、いずれも化合物（１－９）よりも高かった。
実施例２、４、７、８で得られた錯体化合物についても、量子収率の値は比較例１、２で得られた錯体化合物より高かった。
また、実施例２、４、６～８で得られた錯体化合物、及び比較例１、２で得られた錯体化合物を用いてフィルムを作製し、その発光スペクトルを測定したところ、図７～９に示すように、実施例２、４、６～８で得られた錯体化合物を含むフィルムの方が、比較例１、２で得られた錯体化合物を含むフィルムに比べて発光強度が高かった。
以上の結果より、実施例２、４、６～８で得られた錯体化合物の方が比較例１、２で得られた錯体化合物よりも蛍光材料として優れていることが示された。実施例１、３、５で得られた錯体化合物も、実施例２、４、６で得られた錯体化合物と同様の効果を有する。
The complex compound (compound (1-6)) obtained in Example 6 emitted red light in both solid form and in solution when irradiated with ultraviolet rays near the black light wavelength (365 nm). FIG. 5 is an emission spectrum of compound (1-6) in a solution, FIG. 6 is an emission spectrum of a solid of compound (1-6), and FIG. 7 is emission of a film containing compound (1-6). It is a spectrum. As is clear from these FIGS. 5 to 7, compound (1-6) has a sharp emission band having a narrow half width at 614 nm.
On the other hand, the complex compound (compound (1-9)) obtained in Comparative Example 1 also emitted red light in both solid form and in solution when irradiated with ultraviolet rays near the black light wavelength (365 nm). Further, the emission spectrum of the compound (1-9) also shows a spectrum pattern similar to the emission spectrum of the compound (1-6).
However, as is clear from Table 2, when the quantum yields of the solutions of the compound (1-6) and the compound (1-9) are compared, the value of the quantum yield of the compound (1-6) is eventually determined. Was also higher than compound (1-9).
The quantum yield values of the complex compounds obtained in Examples 2, 4, 7 and 8 were also higher than those of the complex compounds obtained in Comparative Examples 1 and 2.
Further, when a film was prepared using the complex compounds obtained in Examples 2, 4, 6 to 8 and the complex compounds obtained in Comparative Examples 1 and 2, and the emission spectra thereof were measured, FIGS. 7 to 9 were taken. As shown in the above, the films containing the complex compounds obtained in Examples 2, 4, 6 to 8 had higher emission intensities than the films containing the complex compounds obtained in Comparative Examples 1 and 2.
From the above results, it was shown that the complex compounds obtained in Examples 2, 4, 6 to 8 are superior to the complex compounds obtained in Comparative Examples 1 and 2 as a fluorescent material. The complex compounds obtained in Examples 1, 3 and 5 have the same effects as the complex compounds obtained in Examples 2, 4 and 6.
本発明の錯体化合物は発光強度が高く、例えばインビジブルインク、発光標識試薬、有機ＥＬ素子、太陽電池の波長変換材料、白色ＬＥＤ等の発光材料として好適である。 The complex compound of the present invention has high emission intensity and is suitable as a light emitting material such as an invisible ink, a light emitting reagent, an organic EL element, a wavelength conversion material for a solar cell, and a white LED.
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