JP6009958B2 - Organometallic complex - Google Patents
Organometallic complex Download PDFInfo
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- JP6009958B2 JP6009958B2 JP2013020801A JP2013020801A JP6009958B2 JP 6009958 B2 JP6009958 B2 JP 6009958B2 JP 2013020801 A JP2013020801 A JP 2013020801A JP 2013020801 A JP2013020801 A JP 2013020801A JP 6009958 B2 JP6009958 B2 JP 6009958B2
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- organometallic complex
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- 125000002524 organometallic group Chemical group 0.000 title claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000004429 atom Chemical group 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 150000008282 halocarbons Chemical group 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Chemical group 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Chemical group 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical group [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000463 material Substances 0.000 description 22
- 125000003118 aryl group Chemical group 0.000 description 21
- -1 phenyloxy group Chemical group 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 125000001769 aryl amino group Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- WVKCLVOFSLNKJP-UHFFFAOYSA-N 2-(2-methyl-1,3-oxazol-4-yl)phenol Chemical compound O1C(C)=NC(C=2C(=CC=CC=2)O)=C1 WVKCLVOFSLNKJP-UHFFFAOYSA-N 0.000 description 4
- GKNCPTLOPRDYMH-UHFFFAOYSA-N 2-bromo-1-(2-methoxyphenyl)ethanone Chemical compound COC1=CC=CC=C1C(=O)CBr GKNCPTLOPRDYMH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 239000003269 fluorescent indicator Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- JWISGKXKSCBIJQ-UHFFFAOYSA-N 2-(1,3-oxazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=COC=N1 JWISGKXKSCBIJQ-UHFFFAOYSA-N 0.000 description 3
- ATWPVFSNULMMQD-UHFFFAOYSA-N 4-(2-methoxyphenyl)-1,3-oxazole Chemical compound COC1=CC=CC=C1C1=COC=N1 ATWPVFSNULMMQD-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000004986 diarylamino group Chemical group 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYLPLPWQCLBGHW-UHFFFAOYSA-N 2-(2-methyl-1,3-thiazol-4-yl)phenol Chemical compound S1C(C)=NC(C=2C(=CC=CC=2)O)=C1 LYLPLPWQCLBGHW-UHFFFAOYSA-N 0.000 description 2
- 0 Cc1*(C)c(-c(cccc2)c2ON2Oc(cccc3)c3-c3c[o]c(C)*23)c[o]1 Chemical compound Cc1*(C)c(-c(cccc2)c2ON2Oc(cccc3)c3-c3c[o]c(C)*23)c[o]1 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GRAMPUYQRIJVPA-UHFFFAOYSA-N OC1=CC=CC=C1C1=CN=C(C=2C=CC=CC=2)N1 Chemical compound OC1=CC=CC=C1C1=CN=C(C=2C=CC=CC=2)N1 GRAMPUYQRIJVPA-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000003145 oxazol-4-yl group Chemical group O1C=NC(=C1)* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical group N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- CSCROCYYYNJFAD-UHFFFAOYSA-N 4-(2-methoxyphenyl)-2-methyl-1,3-oxazole Chemical compound COC1=CC=CC=C1C1=COC(C)=N1 CSCROCYYYNJFAD-UHFFFAOYSA-N 0.000 description 1
- QVFXEBLKPKTMFI-UHFFFAOYSA-N 4-(2-methoxyphenyl)-2-methyl-1,3-thiazole Chemical compound COC1=CC=CC=C1C1=CSC(C)=N1 QVFXEBLKPKTMFI-UHFFFAOYSA-N 0.000 description 1
- JHNNXYPTAHORLW-UHFFFAOYSA-N 5-(2-methoxyphenyl)-2-phenyl-1H-imidazole Chemical compound COC1=CC=CC=C1C1=CNC(C=2C=CC=CC=2)=N1 JHNNXYPTAHORLW-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000005224 alkoxybenzenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000003638 stannyl group Chemical group [H][Sn]([H])([H])* 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Description
本発明は、有機金属錯体に関する。より詳しくは、蛍光を利用する発光材料等として好適に用いることができる有機金属錯体に関する。 The present invention relates to an organometallic complex. More specifically, the present invention relates to an organometallic complex that can be suitably used as a light-emitting material utilizing fluorescence.
有機金属錯体は、例えば蛍光を利用する発光材料等として注目されている。なお、蛍光を利用する発光材料としては、近年では色素レーザー、蛍光顔料、蛍光染料、蛍光マーキング材、蛍光指示薬、セキュリティーインク、センサー等の幅広い用途があり、その需要が拡大している。 An organometallic complex has attracted attention as a light emitting material utilizing fluorescence, for example. In recent years, light emitting materials using fluorescence have a wide range of uses such as dye lasers, fluorescent pigments, fluorescent dyes, fluorescent marking materials, fluorescent indicators, security inks, and sensors, and the demand for these materials is expanding.
従来の有機金属錯体として、ヘテロ原子含有環を有する特定の構造のものを配位子として用い、特定の金属を中心金属原子として用いることが開示されている(例えば、特許文献1〜9、非特許文献1〜6参照。)。 As a conventional organometallic complex, the use of a specific structure having a heteroatom-containing ring as a ligand and the use of a specific metal as a central metal atom is disclosed (for example, Patent Documents 1 to 9, Non-Patent Documents (See Patent Documents 1 to 6.)
有機金属錯体は、配位子及び中心金属原子から構成されるものであり、これらをそれぞれ選択することにより電子軌道等を目的に応じて設計し、その機能を好適に発現させることができる。有機金属錯体は、上述したように、近年では、例えば蛍光を利用する発光材料として、色素レーザー、蛍光顔料、蛍光染料、蛍光マーキング材、蛍光指示薬、セキュリティーインク、センサー等の幅広い用途が期待されている。なお、このような用途に好適に用いられる有機金属錯体のバリエーションを増やすことは、当該有機金属錯体を当該用途において種々の目的で用いる場合に選択の幅を拡げることができ、大きな技術的意義がある。 The organometallic complex is composed of a ligand and a central metal atom, and by selecting each of them, an electron orbit or the like can be designed according to the purpose, and its function can be suitably expressed. As described above, in recent years, organic metal complexes are expected to be used in a wide range of applications such as dye lasers, fluorescent pigments, fluorescent dyes, fluorescent marking materials, fluorescent indicators, security inks, and sensors as light emitting materials that utilize fluorescence. Yes. Increasing variations of organometallic complexes that are suitably used for such applications can broaden the scope of selection when the organometallic complexes are used for various purposes in the applications, and have great technical significance. is there.
数多くの有機化合物、金属錯体が発光材料等として研究されているが、特に青色〜紫色の蛍光を発するものについて、色純度及び材料の安定性を充分なものとすることが難しく、そのために報告例も少なく、更なる開発が望まれている状況である。 Many organic compounds and metal complexes have been studied as luminescent materials, but it is difficult to achieve sufficient color purity and material stability, especially for those emitting blue to violet fluorescence. There are few, and further development is desired.
本発明は、上記現状に鑑みてなされたものであり、錯体としての安定性を充分なものとしながら、特に青色〜紫色の蛍光等を、高い色純度で発することができ、蛍光を利用する発光材料等として好適に用いることができる有機金属錯体を提供することを目的とする。 The present invention has been made in view of the above-mentioned present situation, and is capable of emitting particularly blue to purple fluorescence with high color purity while ensuring sufficient stability as a complex. It is an object to provide an organometallic complex that can be suitably used as a material or the like.
本発明者等は、蛍光を利用する発光材料等として好適に用いることができる化合物について種々検討し、有機金属錯体に着目した。中でも、フェノール環における酸素原子が直接結合した炭素原子の隣の炭素原子に、環構成原子として窒素原子をもつ環が結合した構造のキレート配位子を用いる有機金属錯体に着目した。このような有機金属錯体は、蛍光発光する性質をもつものが多い。そして、中心金属原子の種類を特定し、かつキレート配位子において、窒素原子をもつ環における窒素原子の位置を特定したり、窒素原子をもつ環の置換基どうしが結合して環構造を形成しないものとしたりして窒素原子をもつ環の構造等を更に特定することにより、最高被占軌道(HOMO)と、最低空軌道(LUMO)とのバンドギャップを充分に拡げることができ、青色の蛍光発光材料等として発光の色純度を向上するとともに、錯体の安定性を充分に優れるものとすることができることを見出し、上記課題を見事に解決することができることに想到した。また、このような配位子骨格に結合した水素原子を、他の原子や原子団に置換することができ、それによって様々な構造の有機金属化合物を製造することができることを見出し、本発明に到達したものである。 The inventors of the present invention have studied various compounds that can be suitably used as a light emitting material utilizing fluorescence, and have focused on organometallic complexes. In particular, attention was paid to organometallic complexes using chelate ligands having a structure in which a ring having a nitrogen atom as a ring constituent atom is bonded to a carbon atom adjacent to a carbon atom directly bonded to an oxygen atom in a phenol ring. Many of such organometallic complexes have the property of emitting fluorescence. Then, the type of the central metal atom is specified, and in the chelate ligand, the position of the nitrogen atom in the ring having a nitrogen atom is specified, or the substituents of the ring having a nitrogen atom are combined to form a ring structure. The band gap between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) can be expanded sufficiently by further specifying the structure of the ring having a nitrogen atom, etc. As a fluorescent light-emitting material, etc., it has been found that the color purity of light emission can be improved and the stability of the complex can be sufficiently improved, and the above problem can be solved brilliantly. In addition, the present inventors have found that hydrogen atoms bonded to such a ligand skeleton can be substituted with other atoms or atomic groups, thereby producing organometallic compounds having various structures. It has been reached.
すなわち本発明は、下記一般式(1)で表されることを特徴とする有機金属錯体である。 That is, the present invention is an organometallic complex represented by the following general formula (1).
(式中、Xは、1価の置換基を有していてもよい窒素原子、酸素原子、又は、硫黄原子を表す。中心金属原子Mは、周期表の第1族〜第3族、第12族、又は、第13族に属する金属原子を表す。窒素原子から中心金属原子Mへの矢印は、窒素原子が中心金属原子Mへ配位していることを表す。nは、2又は3である。R1は、Xが1価の置換基を有していてもよい窒素原子、又は、酸素原子である場合は、水素原子又は1価の置換基を表し、Xが硫黄原子である場合は、水素原子又はNH2以外の1価の置換基を表す。R2は、水素原子又は1価の置換基を表す。R3〜R6は、同一又は異なって、水素原子又は1価若しくは2価の置換基を表す。R3〜R6のいずれか2個が2価の置換基を表し、これらが互いに結合して芳香環以外の環構造を形成していてもよい。)
以下に本発明を詳述する。
(In the formula, X represents a nitrogen atom, an oxygen atom, or a sulfur atom which may have a monovalent substituent. The central metal atom M represents groups 1 to 3 and groups 1 and 3 of the periodic table. It represents a metal atom belonging to Group 12 or Group 13. The arrow from the nitrogen atom to the central metal atom M represents that the nitrogen atom is coordinated to the central metal atom M. n is 2 or 3 R 1 represents a hydrogen atom or a monovalent substituent when X is an optionally substituted nitrogen atom or an oxygen atom, and X is a sulfur atom. In the case, it represents a monovalent substituent other than a hydrogen atom or NH 2. R 2 represents a hydrogen atom or a monovalent substituent, and R 3 to R 6 are the same or different and represent a hydrogen atom or a monovalent group. or any two of the .R 3 to R 6 representing a divalent substituent represents a divalent substituent, an aromatic ring or more bonded they together Ring structures may be formed.)
The present invention is described in detail below.
本明細書中、配位しているとは、窒素原子が中心金属原子Mに対して配位子と同様に作用して化学的に影響していることを意味する。 In the present specification, coordinating means that the nitrogen atom acts on the central metal atom M in the same manner as the ligand and has a chemical influence.
本発明の有機金属錯体における上記中心金属原子Mが、ベリリウム、マグネシウム、カルシウム、バリウム、スカンジウム、亜鉛、アルミニウム、又は、ガリウムを表すことが好ましい。より好ましくは、上記中心金属原子Mが、ベリリウム、マグネシウム、亜鉛、又は、アルミニウムを表す。更に好ましくは、上記中心金属原子Mが、マグネシウム、亜鉛、又は、アルミニウムを表す。 The central metal atom M in the organometallic complex of the present invention preferably represents beryllium, magnesium, calcium, barium, scandium, zinc, aluminum or gallium. More preferably, the central metal atom M represents beryllium, magnesium, zinc, or aluminum. More preferably, the central metal atom M represents magnesium, zinc, or aluminum.
本発明の有機金属錯体における上記一般式(1)中、Xが有していてもよい1価の置換基は、炭素数1〜20の炭化水素基、炭素数1〜12のハロゲン化炭化水素基、又は、炭素数0〜12のヘテロ原子含有環基であることが好ましい。より好ましくは、炭素数1〜20の炭化水素基である。
また本発明の有機金属錯体における上記一般式(1)中、R1〜R6は、同一又は異なって、水素原子、ハロゲン原子、炭素数1〜20の炭化水素基、炭素数1〜12のハロゲン化炭化水素基、炭素数0〜12のヘテロ原子含有環基、シアノ基、炭素数1〜12のアルコキシ基、炭素数6〜12のアリールオキシ基、炭素数1〜12のアルキルアミノ基、又は、炭素数6〜18のアリールアミノ基であることが好ましい。これら1価の置換基は、水素原子から置き換わっても、材料劣化や性能の悪化に特に寄与しないものである。また、ヘテロ原子含有環基は、本明細書中、炭素、水素以外の原子であるヘテロ原子を環構成原子として含有する環状の基を言う。
In the above general formula (1) in the organometallic complex of the present invention, the monovalent substituent that X may have is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 12 carbon atoms. It is preferably a group or a hetero atom-containing cyclic group having 0 to 12 carbon atoms. More preferably, it is a C1-C20 hydrocarbon group.
Moreover, in said general formula (1) in the organometallic complex of this invention, R < 1 > -R < 6 > is the same or different, A hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, C1-C12 A halogenated hydrocarbon group, a heteroatom-containing cyclic group having 0 to 12 carbon atoms, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, Or it is preferable that it is a C6-C18 arylamino group. Even if these monovalent substituents are replaced with hydrogen atoms, they do not particularly contribute to material deterioration or performance deterioration. In addition, the hetero atom-containing ring group means a cyclic group containing a hetero atom which is an atom other than carbon and hydrogen as a ring constituent atom.
本発明の有機金属錯体における上記R3〜R6の少なくとも2つが水素原子を表すことが好ましい。より好ましくは、R3〜R6の少なくとも3つが水素原子を表すことである。例えば、上記R4及びR5が同一又は異なって1価の置換基を表し、R3及びR6がそれぞれ水素原子を表すもの、上記R4が1価の置換基を表し、R3、R5及びR6がそれぞれ水素原子を表すもの、上記R5が1価の置換基を表し、R3、R4及びR6がそれぞれ水素原子を表すものがそれぞれ好ましい。特に好ましくは、R3〜R6がそれぞれ水素原子を表すことである。 It is preferable that at least two of the above R 3 to R 6 in the organometallic complex of the present invention represent a hydrogen atom. More preferably, at least three of R 3 to R 6 represent a hydrogen atom. For example, R 4 and R 5 are the same or different and each represents a monovalent substituent, R 3 and R 6 each represent a hydrogen atom, R 4 represents a monovalent substituent, R 3 , R 5 Preferred are those in which 5 and R 6 each represent a hydrogen atom, the above R 5 represents a monovalent substituent, and R 3 , R 4 and R 6 each represent a hydrogen atom. Particularly preferably, R 3 to R 6 each represent a hydrogen atom.
上記ハロゲン原子は、フッ素原子、塩素原子、臭素原子、又は、ヨウ素原子であることが好ましい。
上記炭素数1〜20の炭化水素基は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、オクチル基等の炭素数1〜12の直鎖状若しくは分岐鎖状アルキル基;ビニル基、1−プロペニル基、アリル基、スチリル基等の炭素数2〜12のアルケニル基;エチニル基、1−プロピニル基、プロパルギル基等の炭素数2〜12のアルキニル基;シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数5〜12の環状アルキル基;アルキル基、アルケニル基、アルキニル基等で置換されていてもよい炭素数6〜20のアリール基が挙げられる。
The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
The hydrocarbon group having 1 to 20 carbon atoms is a straight chain having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, and octyl group. C2-C12 alkenyl groups such as vinyl, 1-propenyl, allyl, and styryl groups; C2-C12 such as ethynyl, 1-propynyl, and propargyl groups An alkynyl group; a cyclic alkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; and an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, an alkenyl group, an alkynyl group or the like It is done.
上記炭素数1〜20の炭化水素基は、上述したもののうち、その炭素数が1〜8であることが好ましい。より好ましくは、1〜6である。更に好ましくは、1〜4である。特に好ましくは、1である。 The hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 8 carbon atoms among those described above. More preferably, it is 1-6. More preferably, it is 1-4. Particularly preferred is 1.
上記炭素数1〜12のハロゲン化炭化水素基は、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基等の炭素数1〜12のハロアルキル基;ハロゲン原子で置換された炭素数6〜12のアリール基が挙げられる。
上記炭素数1〜12のハロゲン化炭化水素基は、上述したもののうち、その炭素数が1〜8であることが好ましい。より好ましくは、1〜6である。
The halogenated hydrocarbon group having 1 to 12 carbon atoms is a haloalkyl group having 1 to 12 carbon atoms such as a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group; an aryl having 6 to 12 carbon atoms substituted with a halogen atom Groups.
The halogenated hydrocarbon group having 1 to 12 carbon atoms is preferably 1 to 8 carbon atoms among those described above. More preferably, it is 1-6.
上記炭素数0〜12のヘテロ原子含有環基は、ペンタゾール等の5員環窒素含有環基;トリアゾール、テトラゾール、イミダゾール、オキサゾール、イソオキサゾール、チアゾール、イソチアゾール、ピラゾール、ピロール、ピロリジン、オキサゾリン、フラン、チオフェン等の5員環複素環基;ピリジン、ピラジン、ピペリジン、モルホリン、チアジン等の6員環複素環基が好適なものとして挙げられる。なお、これらヘテロ原子含有環基は、ハロゲン原子やアルキル基、アルコキシ基、アルケニル基、アルキニル基で置換されていてもよい。なお、上記炭素数0〜12のヘテロ原子含有環基は、1つの環構造から構成されるものが好ましく、言い換えれば、複数の環構造を構成しないものが好ましい。
上記炭素数0〜12のヘテロ原子含有環基は、上述したもののうち、その炭素数が1〜8であることが好ましい。より好ましくは、1〜6である。
The hetero atom-containing cyclic group having 0 to 12 carbon atoms is a 5-membered nitrogen-containing cyclic group such as pentazole; triazole, tetrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyrazole, pyrrole, pyrrolidine, oxazoline, furan Preferred examples include 5-membered ring heterocyclic groups such as thiophene; and 6-membered heterocyclic groups such as pyridine, pyrazine, piperidine, morpholine, thiazine and the like. These heteroatom-containing ring groups may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or an alkynyl group. The C 0-12 heteroatom-containing ring group is preferably composed of one ring structure, in other words, it does not constitute a plurality of ring structures.
The C 0-12 heteroatom-containing cyclic group preferably has 1-8 carbon atoms among those described above. More preferably, it is 1-6.
上記炭素数1〜12のアルコキシ基は、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、tert−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基等の直鎖状又は分岐鎖状のものが好適なものとして挙げられる。
上記炭素数1〜12のアルコキシ基は、上述したもののうち、その炭素数が1〜8であることが好ましい。より好ましくは、1〜6である。更に好ましくは、1〜3である。
The alkoxy group having 1 to 12 carbon atoms is methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group A straight chain or branched chain such as is preferable.
It is preferable that the said C1-C12 alkoxy group is C1-C8 among what was mentioned above. More preferably, it is 1-6. More preferably, it is 1-3.
上記炭素数6〜12のアリールオキシ基としては、フェニルオキシ基、ベンジルオキシ基等が挙げられる。上記炭素数6〜12のアリールオキシ基は、例えば、アリールオキシ基のアリール基部分がハロゲン原子やアルキル基、アルコキシ基、アルケニル基、アルキニル基等で置換されていてもよい。
上記炭素数6〜12のアリールオキシ基は、上述したもののうち、その炭素数が6〜10であることが好ましい。より好ましくは、6〜8である。更に好ましくは、6である。
Examples of the aryloxy group having 6 to 12 carbon atoms include a phenyloxy group and a benzyloxy group. In the aryloxy group having 6 to 12 carbon atoms, for example, the aryl group portion of the aryloxy group may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or the like.
Among the above-mentioned aryloxy groups having 6 to 12 carbon atoms, those having 6 to 10 carbon atoms are preferable. More preferably, it is 6-8. More preferably, it is 6.
上記炭素数1〜12のアルキルアミノ基としては、メチルアミノ基、エチルアミノ基等の炭素数1〜12のモノアルキルアミノ基;ジメチルアミノ基、ジエチルアミノ基、ピロジニル基、モルホリニル基等の炭素数2〜12の非環状又は環状ジアルキルアミノ基が好適なものとして挙げられる。
上記炭素数1〜12のアルキルアミノ基は、上述したもののうち、その炭素数が1〜8であることが好ましい。より好ましくは、1〜6である。更に好ましくは、1〜4である。
Examples of the alkylamino group having 1 to 12 carbon atoms include monoalkylamino groups having 1 to 12 carbon atoms such as a methylamino group and an ethylamino group; and 2 carbon atoms such as a dimethylamino group, a diethylamino group, a pyrrolidinyl group, and a morpholinyl group. -12 acyclic or cyclic dialkylamino groups are preferred.
It is preferable that the said C1-C12 alkylamino group is C1-C8 among what was mentioned above. More preferably, it is 1-6. More preferably, it is 1-4.
上記炭素数6〜18のアリールアミノ基としては、フェニルアミノ基、ベンジルアミノ基等の炭素数6〜18のモノアリールアミノ基;N−メチル−N−フェニルアミノ基等のN−アルキル−N−アリールアミノ基;ジフェニルアミノ基、カルバゾリル基、フェノキサジニル基、フェノチアジニル基等の炭素数12〜18の非環状又は環状ジアリールアミノ基等が好適なものとして挙げられる。なお、非環状ジアリールアミノ基とは、芳香環以外の環構造を有しないものをいい、環状ジアリールアミノ基とは、芳香環以外の環構造を有するものをいう。上記炭素数6〜18のアリールアミノ基は、例えば、アリールアミノ基のアリール基部分がハロゲン原子やアルキル基、アルコキシ基、アルケニル基、アルキニル基等で置換されていてもよい。
上記炭素数6〜18のアリールアミノ基は、上述したもののうち、その炭素数が8〜18であることが好ましい。より好ましくは、12〜18である。更に好ましくは、12である。
Examples of the arylamino group having 6 to 18 carbon atoms include monoarylamino groups having 6 to 18 carbon atoms such as phenylamino group and benzylamino group; N-alkyl-N— such as N-methyl-N-phenylamino group. Preferred examples include arylamino groups; acyclic or cyclic diarylamino groups having 12 to 18 carbon atoms such as diphenylamino group, carbazolyl group, phenoxazinyl group, and phenothiazinyl group. The acyclic diarylamino group means a group having no ring structure other than an aromatic ring, and the cyclic diarylamino group means a group having a ring structure other than an aromatic ring. In the arylamino group having 6 to 18 carbon atoms, for example, the aryl group portion of the arylamino group may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or the like.
Of the above-mentioned arylamino groups having 6 to 18 carbon atoms, those having 8 to 18 carbon atoms are preferable. More preferably, it is 12-18. More preferably, it is 12.
その他、上記R1〜R6における1価の置換基は、アセチル基、プロピオニル基、ブチリル基等のアシル基;N,N−ジメチルカルバモイル基、N,N−ジエチルカルバモイル基等のN,N−ジアルキルカルバモイル基;チオアセチル基、チオベンゾイル基、メトキシチオカルボニル基等のチオカルボニル基;ジオキサボロラニル基、スタニル基、シリル基、エステル基、ホルミル基、チオエーテル基、エポキシ基、イソシアネート基、ヒドロキシル基、スルホ基、スルホニル基、ホスホリル基、カルボキシル基等であってもよい。 In addition, the monovalent substituents in R 1 to R 6 are acyl groups such as acetyl group, propionyl group and butyryl group; N, N— such as N, N-dimethylcarbamoyl group and N, N-diethylcarbamoyl group. Dialkylcarbamoyl group; thiocarbonyl group such as thioacetyl group, thiobenzoyl group, methoxythiocarbonyl group; dioxaborolanyl group, stannyl group, silyl group, ester group, formyl group, thioether group, epoxy group, isocyanate group, hydroxyl group It may be a group, a sulfo group, a sulfonyl group, a phosphoryl group, a carboxyl group, or the like.
なお、上記R1〜R6における1価の置換基は、本発明の効果を発揮できる限り、ハロゲン原子やヘテロ原子、アルキル基、アルコキシ基、アルケニル基、アルキニル基、芳香環等で置換されていてもよい。また、上記アルキル基、アリール基やヘテロ原子含有環基等が置換され、1価の置換基を有する場合(上記1価の置換基が更に1価の置換基を有する場合)、1価の置換基が結合する位置や数は特に限定されない。 The monovalent substituents in R 1 to R 6 are substituted with a halogen atom, a hetero atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aromatic ring, or the like as long as the effects of the present invention can be exhibited. May be. In addition, when the alkyl group, aryl group, heteroatom-containing ring group or the like is substituted and has a monovalent substituent (when the monovalent substituent further has a monovalent substituent), monovalent substitution There are no particular restrictions on the position or number of groups to which the group is bonded.
これらの中でも、上記R1〜R6における1価の置換基は、炭素数1〜12の炭化水素基、又は、炭素数1〜12のハロゲン化炭化水素基であることが好ましい。上記炭素数1〜12の炭化水素基は、上記炭素数1〜12の直鎖状若しくは分岐鎖状アルキル基、又は、上記炭素数6〜12のアリール基であることがより好ましい。上記炭素数1〜12のハロゲン化炭化水素基は、上記炭素数1〜12のフッ化炭化水素基であることがより好ましい。更に好ましくは、トリフルオロメチル基である。 Among these, the monovalent substituent in R 1 to R 6 is preferably a hydrocarbon group having 1 to 12 carbon atoms or a halogenated hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group having 1 to 12 carbon atoms is more preferably the linear or branched alkyl group having 1 to 12 carbon atoms or the aryl group having 6 to 12 carbon atoms. The halogenated hydrocarbon group having 1 to 12 carbon atoms is more preferably the fluorinated hydrocarbon group having 1 to 12 carbon atoms. More preferably, it is a trifluoromethyl group.
なお、上記一般式(1)で表される有機金属錯体では、上記R3〜R6のいずれか2個が2価の置換基を表し、これらが互いに結合して芳香環以外の環構造を形成していてもよい。すなわち、上記R3〜R6のいずれか2個が、互いに共有結合により結合するとともに、上記一般式(1)中に示したフェノール環を構成する炭素原子とも結合する、2価の置換基を表すものであってもよい。このとき、上記2個の2価の置換基は、当該2個の2価の置換基が結合している該フェノール環の炭素原子と共に芳香環以外の環構造を形成する。該芳香環以外の環構造は、該フェノール環との間で共役系を構成する多重結合を有さないものであればよい。本発明の有機金属錯体は、このような構成により、青色蛍光等を高い色純度で発することができる。また、該芳香環以外の環構造は、炭素原子だけから構成されることが好ましい。言い換えれば、該芳香環以外の環構造は、ヘテロ原子含有環構造ではないことが好ましい。 In the organometallic complex represented by the general formula (1), any two of R 3 to R 6 represent a divalent substituent, and these are bonded to each other to form a ring structure other than an aromatic ring. It may be formed. That is, any two of R 3 to R 6 are bonded to each other by a covalent bond and a divalent substituent that is also bonded to the carbon atom constituting the phenol ring shown in the general formula (1). It may represent. At this time, the two divalent substituents together with the carbon atom of the phenol ring to which the two divalent substituents are bonded form a ring structure other than the aromatic ring. Any ring structure other than the aromatic ring may be used as long as it does not have multiple bonds constituting a conjugated system with the phenol ring. With such a configuration, the organometallic complex of the present invention can emit blue fluorescence or the like with high color purity. Moreover, it is preferable that ring structures other than this aromatic ring are comprised only from a carbon atom. In other words, the ring structure other than the aromatic ring is preferably not a heteroatom-containing ring structure.
上記芳香環以外の環構造は、例えば、5員環〜7員環であることが好ましい。より好ましくは、6員環である。上記芳香環以外の環構造を構成する原子は、それぞれ、同一又は異なって、水素原子又は1価の置換基を有する。上記芳香環以外の環構造を構成する原子が1価の置換基を有する場合は、該1価の置換基の好ましい構成は、上述した1価の置換基の好ましい構成と同様である。また、上記芳香環以外の環構造を構成する原子は、それぞれ、水素原子を有することが特に好ましい。 The ring structure other than the aromatic ring is preferably a 5- to 7-membered ring, for example. More preferably, it is a 6-membered ring. The atoms constituting the ring structure other than the aromatic ring are the same or different and have a hydrogen atom or a monovalent substituent. When the atoms constituting the ring structure other than the aromatic ring have a monovalent substituent, the preferred configuration of the monovalent substituent is the same as the preferred configuration of the monovalent substituent described above. Moreover, it is especially preferable that each atom constituting the ring structure other than the aromatic ring has a hydrogen atom.
上記2価の置換基は、例えば、上述した1価の置換基において水素原子を有するものに対応するものであることが好ましい。すなわち、該1価の置換基として水素原子を有するものから水素原子を1つ脱離した構造のものを用いることができる。このような置換基もまた、材料劣化や性能の悪化に特に寄与しないものである。 The divalent substituent preferably corresponds to, for example, the above-described monovalent substituent having a hydrogen atom. That is, a structure in which one hydrogen atom is eliminated from one having a hydrogen atom as the monovalent substituent can be used. Such substituents also do not particularly contribute to material deterioration or performance deterioration.
なお、Xが有していてもよい置換基、及び、R1、R2における置換基が1価の置換基であるということは、これらの置換基どうしが結合しておらず、縮環構造を形成していないことを意味する。また、これらの置換基と、R3〜R6の置換基とが結合しておらず、縮環構造を形成していないことを意味する。更に、上記一般式(1)で表される有機金属錯体は、通常、別の有機金属錯体と、置換基等を介して共有結合により結合されていない。本発明の有機金属錯体は、このような構成により、青色蛍光等を高い色純度で発することができる。 In addition, the substituent which X may have and the substituents in R 1 and R 2 are monovalent substituents means that these substituents are not bonded to each other, and a condensed ring structure. Does not form. Moreover, these substituents and the substituent of R < 3 > -R < 6 > are not couple | bonded, and it means that the condensed ring structure is not formed. Furthermore, the organometallic complex represented by the general formula (1) is usually not bonded to another organometallic complex by a covalent bond via a substituent or the like. With such a configuration, the organometallic complex of the present invention can emit blue fluorescence or the like with high color purity.
本発明の有機金属錯体における1価の置換基、2価の置換基について詳細に説明したが、上記Xは、1価の置換基を有する窒素原子、酸素原子又は硫黄原子であることが好ましい。また、R1及びR2は、同一又は異なって、水素原子、又は、炭素数1〜4の直鎖状若しくは分岐鎖状アルキル基を表すことが好ましい。より好ましくは、例えば、R1及びR2が、それぞれ、水素原子を表すか、又は、R1がメチル基を表し、R2が水素原子を表すことである。 Although the monovalent substituent and the divalent substituent in the organometallic complex of the present invention have been described in detail, X is preferably a nitrogen atom, an oxygen atom or a sulfur atom having a monovalent substituent. R 1 and R 2 are the same or different and preferably represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, for example, R 1 and R 2 each represent a hydrogen atom, or R 1 represents a methyl group and R 2 represents a hydrogen atom.
また上記X1における1価の置換基、R1、及び、R2の少なくとも1つが、炭素数6〜12のアリール基であることが本発明のもう1つの好ましい形態である。更に好ましくは、上記X1における1価の置換基、R1、及び、R2の少なくとも1つが、フェニル基又はナフチル基であることである。上記X1における1価の置換基、R1、及び、R2の少なくとも1つがフェニル基やナフチル基である場合のように、芳香環を、本発明の金属錯体の複素環に直接結合させることで、本発明の効果を発揮できるとともに、耐熱性を際立って優れたものとすることができる。例えば、R1がフェニル基を表し、R2が水素原子を表すことが特に好ましい。 In addition, in another preferred embodiment of the present invention, at least one of the monovalent substituent, R 1 and R 2 in X 1 is an aryl group having 6 to 12 carbon atoms. More preferably, at least one of the monovalent substituent, R 1 and R 2 in X 1 is a phenyl group or a naphthyl group. The monovalent substituent in X 1, R 1, and, as in the case at least one of R 2 is a phenyl group or a naphthyl group, it is attached directly to the aromatic ring, a heterocyclic ring of the metal complexes of the present invention Thus, the effects of the present invention can be exhibited and the heat resistance can be remarkably improved. For example, it is particularly preferable that R 1 represents a phenyl group and R 2 represents a hydrogen atom.
上記一般式(1)におけるnは、2又は3であり、該数は、通常は金属原子の価数によって決まる。言い換えれば、上記一般式(1)で表される有機金属錯体の配位子は2つ又は3つある。これらは同一であってもよく、異なっていてもよいが、同一であることが好ましい。また、nが2であることが好ましい。 In the general formula (1), n is 2 or 3, and the number is usually determined by the valence of the metal atom. In other words, there are two or three ligands of the organometallic complex represented by the general formula (1). These may be the same or different, but are preferably the same. Further, n is preferably 2.
本発明の有機金属錯体は、通常用いられる種々の手法により合成できる。本発明の有機金属錯体に係る配位子は、例えば、該配位子のフェノール環の酸素原子がアルコキシ化された化合物(以下、アルコキシ体とも言う。)を経て製造することができる。
上記アルコキシ体は、例えば、環構成原子として窒素原子をもつ5員環の芳香族化合物と、オルト位の炭素上の水素がハロゲン原子等の反応性基に置換されたフェノールとを有機溶媒等の溶媒中で触媒の存在下反応させることにより得ることができる。また、オルト位の炭素上に置換基を有するアルコキシベンゼンにおいて、該置換基の一部を環化させて得ることもできる。
The organometallic complex of the present invention can be synthesized by various commonly used techniques. The ligand according to the organometallic complex of the present invention can be produced, for example, via a compound in which the oxygen atom of the phenol ring of the ligand is alkoxylated (hereinafter also referred to as an alkoxy form).
The above alkoxy compound is, for example, an organic solvent such as a 5-membered aromatic compound having a nitrogen atom as a ring constituent atom and a phenol in which hydrogen on the ortho-position carbon is substituted with a reactive group such as a halogen atom. It can obtain by making it react in presence of a catalyst in a solvent. Moreover, in the alkoxybenzene which has a substituent on the carbon of ortho position, it can also obtain by cyclizing a part of this substituent.
本発明の有機金属錯体に係る配位子は、上記アルコキシ体において、アルコキシ基を種々の反応試薬を用いて脱アルキル化反応させることにより得ることができる。また、オルト位の炭素上に置換基を有するフェノールにおいて、該置換基の一部を環化させて得ることもできる。
本発明の有機金属錯体は、上記配位子を、金属塩と中性若しくは塩基性条件下で反応させることにより得ることができる。ただし、本発明の有機金属錯体の製造方法は、これに制限されない。
The ligand according to the organometallic complex of the present invention can be obtained by dealkylating an alkoxy group using various reaction reagents in the above alkoxy body. Moreover, in the phenol which has a substituent on the carbon of ortho position, it can also obtain by cyclizing a part of this substituent.
The organometallic complex of the present invention can be obtained by reacting the above ligand with a metal salt under neutral or basic conditions. However, the manufacturing method of the organometallic complex of this invention is not restrict | limited to this.
本発明の有機金属錯体は、例えば蛍光を利用する発光材料等として好適に用いることができるものである。蛍光を利用する発光材料としては、色素レーザー、蛍光顔料、蛍光染料、蛍光マーキング材、蛍光指示薬、セキュリティーインク、センサー等が特に好適なものとして挙げられる。 The organometallic complex of the present invention can be suitably used as, for example, a light emitting material utilizing fluorescence. As a light emitting material using fluorescence, a dye laser, a fluorescent pigment, a fluorescent dye, a fluorescent marking material, a fluorescent indicator, a security ink, a sensor, and the like are particularly preferable.
青色〜紫色を発光する発光材料として好適に用いるうえでは、蛍光分光分析において蛍光発光波長が360〜480nmの範囲にあることが好ましい。また、本発明の有機金属錯体の最高被占軌道(HOMO)のエネルギー準位と、本発明の有機金属錯体の最低空軌道(LUMO)のエネルギー準位との差(バンドギャップ)が、2.6eV以上であることが好ましい。より好ましくは、2.8eV以上である。該差は、4.0eV以下であることが好ましい。
本発明の有機金属錯体のHOMOとLUMOのエネルギー準位の差は、紫外可視分光分析(UV−Vis)により測定する方法で評価することができる。
When used suitably as a light emitting material that emits blue to purple light, the fluorescence emission wavelength is preferably in the range of 360 to 480 nm in fluorescence spectroscopic analysis. The difference (band gap) between the energy level of the highest occupied orbital (HOMO) of the organometallic complex of the present invention and the energy level of the lowest unoccupied orbital (LUMO) of the organometallic complex of the present invention is 2. It is preferable that it is 6 eV or more. More preferably, it is 2.8 eV or more. The difference is preferably 4.0 eV or less.
The difference between the energy levels of HOMO and LUMO of the organometallic complex of the present invention can be evaluated by a method of measuring by ultraviolet-visible spectroscopy (UV-Vis).
本発明の有機金属錯体は、錯体としての安定性に優れるとともに、例えば青色の蛍光等を、高い色純度で発することができ、色素レーザー、蛍光顔料、蛍光染料、蛍光マーキング材、蛍光指示薬、セキュリティーインク、センサー等の、蛍光を利用する発光材料等として好適に用いることができる。 The organometallic complex of the present invention is excellent in stability as a complex, and can emit, for example, blue fluorescence with high color purity, such as dye laser, fluorescent pigment, fluorescent dye, fluorescent marking material, fluorescent indicator, security It can be suitably used as a light emitting material utilizing fluorescence, such as ink and sensor.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「%」は「質量%」を意味するものとする。また、本明細書中、「置換」、「置換基」は、それぞれ、水素原子以外の原子又は原子団による置換、そのような置換をしたかたちの基を言う。更に、「フェノール環」は、フェノール基において、そのヒドロキシル基から水素原子が脱離したかたちのものも含む。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified. Further, in the present specification, “substitution” and “substituent” refer to substitution with an atom or atomic group other than a hydrogen atom, and a group having such substitution, respectively. Further, the “phenol ring” includes a phenol group in which a hydrogen atom is eliminated from its hydroxyl group.
なお、蛍光は、励起一重項状態からの発光である。一般的に物質に光又は電気エネルギーが加わると基底状態と呼ばれる状態から励起された状態へと電子状態が変化する(この過程を励起と呼ぶ。)。なお、励起された状態には一重項励起状態と三重項励起状態との2種類がある。本発明の有機金属化合物に、常温で光エネルギーを加えた場合は、通常は100%一重項励起状態に励起する。本発明の上述した用途では、光エネルギーを加えて得られる発光を利用するものがほとんどであると考えられる。 Note that fluorescence is light emission from an excited singlet state. In general, when light or electric energy is applied to a substance, the electronic state changes from a state called a ground state to an excited state (this process is called excitation). There are two types of excited states, a singlet excited state and a triplet excited state. When light energy is applied to the organometallic compound of the present invention at room temperature, it is normally excited to a 100% singlet excited state. In the above-described uses of the present invention, it is considered that most of the uses utilize light emission obtained by adding light energy.
実施例において合成した化合物についての各種測定は、以下のように行った。
(1H−NMR測定)
試料をテトラメチルシランを含有する重クロロホルムまたは重ジメチルスルホキシドに溶解し、核磁気共鳴装置(Gemini2000、400MHz、Varian社製)により測定した。
(蛍光スペクトル測定)
試料をジメチルホルムアミドの希薄溶液とし、蛍光分光光度計(F−7000、日立ハイテクノロジーズ社製)を用いて、蛍光スペクトルを測定した。励起波長は350nmとし、発光強度が最大となるところを蛍光波長(λmax)とした。
Various measurements on the compounds synthesized in the examples were performed as follows.
(1 H-NMR measurement)
The sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide containing tetramethylsilane and measured with a nuclear magnetic resonance apparatus (Gemini 2000, 400 MHz, manufactured by Varian).
(Fluorescence spectrum measurement)
The sample was used as a dilute solution of dimethylformamide, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (F-7000, manufactured by Hitachi High-Technologies Corporation). The excitation wavelength was 350 nm, and the place where the emission intensity was maximum was the fluorescence wavelength (λmax).
(実施例1)2−(オキサゾール−4−イル)フェノラト亜鉛(II)
4−(2−メトキシフェニル)オキサゾール
Example 1 2- (Oxazol-4-yl) phenolatozinc (II)
4- (2-methoxyphenyl) oxazole
2−ブロモ−1−(2−メトキシフェニル)エタノン(3.0g,13mmol)をホルムアミド(50ml)に溶解し、100℃で24時間反応させた。反応後、クロロホルム(300ml)に溶解し、水洗し、有機層を回収、硫酸ナトリウムで乾燥させた。濾過により硫酸ナトリウムを除き、濃縮し残分をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=1:1)により精製し、目的物を1.5g(収率66%)得た。
1H−NMR(400MHz,CDCl3):δ3.97(s,3H),6.98(d,1H),7.08(t,1H),7.31(t,1H),7.92(s,1H),8.14(d,1H),8.20(s,1H)
2-Bromo-1- (2-methoxyphenyl) ethanone (3.0 g, 13 mmol) was dissolved in formamide (50 ml) and reacted at 100 ° C. for 24 hours. After the reaction, it was dissolved in chloroform (300 ml), washed with water, and the organic layer was collected and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 1.5 g (yield 66%) of the desired product.
1 H-NMR (400 MHz, CDCl 3 ): δ 3.97 (s, 3H), 6.98 (d, 1H), 7.08 (t, 1H), 7.31 (t, 1H), 7.92 (S, 1H), 8.14 (d, 1H), 8.20 (s, 1H)
2−(オキサゾール−4−イル)フェノール 2- (Oxazol-4-yl) phenol
4−(2−メトキシフェニル)オキサゾール(2.6g,15mmol)を脱水ジクロロメタン(30ml)に溶解し、−78℃のドライアイス−アセトンバスで冷却した。そこに三臭化ホウ素(1.0Mジクロロメタン溶液,30ml,30mmol)を静かに滴下した。その後室温まで昇温し、24時間反応させた。反応後、反応液を氷冷し、水を加えクエンチを行った。クロロホルム(200ml)に溶解し、水洗し、有機層を回収、硫酸ナトリウムで乾燥させた。濾過により硫酸ナトリウムを除き、濃縮し残分をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=1:1)により精製し、目的物を1.6g(収率66%)得た。
1H−NMR(400MHz,DMSO−d6):δ6.88−6.94(m,2H),7.14(t,1H),7.89(d,1H),8.36(s,1H),8.42(d,1H),10.27(s,1H)
4- (2-methoxyphenyl) oxazole (2.6 g, 15 mmol) was dissolved in dehydrated dichloromethane (30 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1.0 M dichloromethane solution, 30 ml, 30 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and reacted for 24 hours. After the reaction, the reaction solution was ice-cooled and quenched by adding water. Dissolved in chloroform (200 ml) and washed with water, the organic layer was recovered and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 1.6 g (yield 66%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 6.88-6.94 (m, 2H), 7.14 (t, 1H), 7.89 (d, 1H), 8.36 (s, 1H), 8.42 (d, 1H), 10.27 (s, 1H)
2−(オキサゾール−4−イル)フェノラト亜鉛(II) 2- (Oxazol-4-yl) phenolatozinc (II)
2−(オキサゾール−4−イル)フェノール(1.6g,10mmol)、塩化亜鉛(II)(681mg,5.0mmol)をメタノール(50ml)に溶解し、室温で10分間撹拌した。そこにトリエチルアミン(1.4ml,10mmol)を加え24時間反応させた。反応後析出固体を減圧濾過で回収、メタノールで洗浄し目的物を1.0g(収率52%)得た。
1H−NMR(400MHz,DMSO−d6):δ6.46(br,2H),6.76(br,2H),7.49(br,2H),8.59(br,2H),8.68(br,2H)
PL(HITACHI F−7000,DMF,Ek=350nm):λmax=383nm
2- (Oxazol-4-yl) phenol (1.6 g, 10 mmol) and zinc chloride (II) (681 mg, 5.0 mmol) were dissolved in methanol (50 ml) and stirred at room temperature for 10 minutes. Triethylamine (1.4 ml, 10 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 1.0 g of the desired product (yield 52%).
1 H-NMR (400 MHz, DMSO-d 6 ): δ 6.46 (br, 2H), 6.76 (br, 2H), 7.49 (br, 2H), 8.59 (br, 2H), 8 .68 (br, 2H)
PL (HITACHI F-7000, DMF, Ek = 350 nm): λmax = 383 nm
(実施例2)2−(2−メチルオキサゾール−4−イル)フェノラト亜鉛(II)
4−(2−メトキシフェニル)−2−メチルオキサゾール
Example 2 2- (2-Methyloxazol-4-yl) phenolato zinc (II)
4- (2-methoxyphenyl) -2-methyloxazole
2−ブロモ−1−(2−メトキシフェニル)エタノン(3.44g,15mmol)をアセトアミド(50g)に溶解し、100℃で24時間反応させた。反応後、クロロホルム(300ml)に溶解し、水洗し、有機層を回収、硫酸ナトリウムで乾燥させた。濾過により硫酸ナトリウムを除き、濃縮し残分をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=1:1)により精製し、目的物を2.1g(収率73%)得た。
1H−NMR(400MHz,CDCl3):δ2.51(s,3H),3.95(s,3H),6.95(d,1H),7.05(t,1H),7.27(t,2H),8.04(s,1H),8.07,(d,1H)
2-Bromo-1- (2-methoxyphenyl) ethanone (3.44 g, 15 mmol) was dissolved in acetamide (50 g) and reacted at 100 ° C. for 24 hours. After the reaction, it was dissolved in chloroform (300 ml), washed with water, and the organic layer was collected and dried over sodium sulfate. The sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 2.1 g (yield 73%) of the desired product.
1 H-NMR (400 MHz, CDCl 3 ): δ 2.51 (s, 3H), 3.95 (s, 3H), 6.95 (d, 1H), 7.05 (t, 1H), 7.27 (T, 2H), 8.04 (s, 1H), 8.07, (d, 1H)
2−(2−メチルオキサゾール−4−イル)フェノール 2- (2-Methyloxazol-4-yl) phenol
4−(2−メトキシフェニル)−2−メチルオキサゾール(4.1g,22mmol)を脱水ジクロロメタン(44ml)に溶解し、−78℃のドライアイス−アセトンバスで冷却した。そこに三臭化ホウ素(1.0Mジクロロメタン溶液,44ml,44mmol)を静かに滴下した。その後室温まで昇温し、24時間反応させた。反応後、反応液を氷冷し、水を加えクエンチを行った。クロロホルム(200ml)に溶解し、水洗し、有機層を回収、硫酸ナトリウムで乾燥させた。濾過により硫酸ナトリウムを除き、濃縮し残分をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=1:1)により精製し、目的物を2.1g(収率55%)得た。
1H−NMR(400MHz,DMSO−d6):δ2.44(s,3H),6.83(t,1H),6.92(d,1H),7.10(t,1H),7.83(d,1H),8.22(s,1H),10.23(s,1H)
4- (2-methoxyphenyl) -2-methyloxazole (4.1 g, 22 mmol) was dissolved in dehydrated dichloromethane (44 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1.0 M dichloromethane solution, 44 ml, 44 mmol) was slowly added dropwise thereto. Thereafter, the temperature was raised to room temperature and reacted for 24 hours. After the reaction, the reaction solution was ice-cooled and quenched by adding water. Dissolved in chloroform (200 ml) and washed with water, the organic layer was recovered and dried over sodium sulfate. Sodium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 2.1 g (yield 55%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 2.44 (s, 3H), 6.83 (t, 1H), 6.92 (d, 1H), 7.10 (t, 1H), 7 .83 (d, 1H), 8.22 (s, 1H), 10.23 (s, 1H)
ビス2−(2−メチルオキサゾール−4−イル)フェノラト亜鉛(II) Bis 2- (2-methyloxazol-4-yl) phenolato zinc (II)
2−(2−メチルオキサゾール−4−イル)フェノール(1.1g,6mmol)、塩化亜鉛(II)(610mg,4.5mmol)をメタノール(30ml)に溶解し、室温で10分間撹拌した。そこにトリエチルアミン(1.0ml,7.2mmol)を加え24時間反応させた。反応後析出固体を減圧濾過で回収、メタノールで洗浄し目的物を700mg(収率56%)得た。
1H−NMR(400MHz,DMSO−d6):δ2.58(s,6H),6.41(t,2H),6.60(d,2H),6.96(t,2H),7.40(d,2H),8.46(s,2H)
PL(HITACHI F−7000,DMF,Ek=350nm):λmax=378nm
2- (2-Methyloxazol-4-yl) phenol (1.1 g, 6 mmol) and zinc (II) chloride (610 mg, 4.5 mmol) were dissolved in methanol (30 ml) and stirred at room temperature for 10 minutes. Triethylamine (1.0 ml, 7.2 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 700 mg (yield 56%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 2.58 (s, 6H), 6.41 (t, 2H), 6.60 (d, 2H), 6.96 (t, 2H), 7 .40 (d, 2H), 8.46 (s, 2H)
PL (HITACHI F-7000, DMF, Ek = 350 nm): λmax = 378 nm
(実施例3)ビス2−(2−メチルオキサゾール−4−イル)フェノラトマグネシウム(II) Example 3 Bis 2- (2-methyloxazol-4-yl) phenolatomagnesium (II)
2−(2−メチルオキサゾール−4−イル)フェノール(300mg,1.7mmol)、塩化マグネシウム(II)六水和物(260mg,1.3mmol)をメタノール(8.5ml)に溶解し、室温で10分間撹拌した。そこにトリエチルアミン(0.24ml,1.6mmol)を加え24時間反応させた。反応後析出固体を減圧濾過で回収、メタノールで洗浄し目的物を100mg(収率32%)得た。
1H−NMR(400MHz,DMSO−d6):δ2.41(s,6H),6.71(br,2H),6.85(br,2H),7.02(br,2H),7.77(br,2H),8.23(br,2H)
PL(HITACHI F−7000,DMF,Ek=350nm):λmax=388nm
2- (2-Methyloxazol-4-yl) phenol (300 mg, 1.7 mmol) and magnesium (II) chloride hexahydrate (260 mg, 1.3 mmol) were dissolved in methanol (8.5 ml) at room temperature. Stir for 10 minutes. Triethylamine (0.24 ml, 1.6 mmol) was added thereto and reacted for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 100 mg (yield 32%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 2.41 (s, 6H), 6.71 (br, 2H), 6.85 (br, 2H), 7.02 (br, 2H), 7 .77 (br, 2H), 8.23 (br, 2H)
PL (HITACHI F-7000, DMF, Ek = 350 nm): λmax = 388 nm
(実施例4)トリス2−(2−メチルオキサゾール−4−イル)フェノラトアルミニウム(III) Example 4 Tris 2- (2-methyloxazol-4-yl) phenolatoaluminum (III)
2−(2−メチルオキサゾール−4−イル)フェノール(300mg,1.7mmol)、アルミニウムイソプロポキシド(120mg,0.6mmol)を脱水THF(3.4ml)に溶解し、2時間環流反応させた。2時間後、室温まで冷却し、さらに24時間室温で反応させた。反応後析出固体を減圧濾過で回収、メタノールで洗浄し目的物を100mg(収率32%)得た。
PL(HITACHI F−7000,DMF,Ek=350nm):λmax=391nm
2- (2-Methyloxazol-4-yl) phenol (300 mg, 1.7 mmol) and aluminum isopropoxide (120 mg, 0.6 mmol) were dissolved in dehydrated THF (3.4 ml) and refluxed for 2 hours. . After 2 hours, the mixture was cooled to room temperature and further reacted at room temperature for 24 hours. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 100 mg (yield 32%) of the desired product.
PL (HITACHI F-7000, DMF, Ek = 350 nm): λmax = 391 nm
(実施例5)ビス2−(2−メチルチアゾール−4−イル)フェノラト亜鉛(II)
4−(2−メトキシフェニル)−2−メチルチアゾール
Example 5 Bis 2- (2-methylthiazol-4-yl) phenolato zinc (II)
4- (2-methoxyphenyl) -2-methylthiazole
2−ブロモ−1−(2−メトキシフェニル)エタノン(4.64g,20.2mmol)とチオアセトアミド(1.67g)をエタノール(100ml)に溶解し、還流させながら加熱し24時間反応させた。反応後、クロロホルムに溶解し、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄した。有機層を硫酸マグネシウムで乾燥させた。濾過により硫酸マグネシウムを除き、濃縮し残渣をシリカゲルカラムクロマトグラフィーにより精製し、目的物を4.0g(収率86%)得た。
1H−NMR(400MHz,CDCl3):δ3.36(s,3H),3.98(s,3H)7.04(d,1H),7.17(t,1H),7.47(t,1H),7.83(s,1H),8.28(d,1H)
2-Bromo-1- (2-methoxyphenyl) ethanone (4.64 g, 20.2 mmol) and thioacetamide (1.67 g) were dissolved in ethanol (100 ml), heated to reflux and allowed to react for 24 hours. After the reaction, the reaction mixture was dissolved in chloroform and washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic layer was dried with magnesium sulfate. The magnesium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.0 g (yield 86%) of the desired product.
1 H-NMR (400 MHz, CDCl 3 ): δ 3.36 (s, 3H), 3.98 (s, 3H) 7.04 (d, 1H), 7.17 (t, 1H), 7.47 ( t, 1H), 7.83 (s, 1H), 8.28 (d, 1H)
2−(2−メチルチアゾール−4−イル)フェノール 2- (2-Methylthiazol-4-yl) phenol
4−(2−メトキシフェニル)−2−メチルチアゾール(4.82g,23.5mmol)を脱水ジクロロメタン(117ml)に溶解し、−78℃のドライアイス−アセトンバスで冷却した。そこに三臭化ホウ素(1Mジクロロメタン溶液,26ml,25.8mmol)を静かに滴下した。その後室温まで昇温し、終夜反応させた。反応後、反応液を氷冷し、炭酸水素ナトリウム水溶液を加えクエンチを行った。クロロホルムで抽出し、有機層を飽和食塩水で洗浄後、硫酸マグネシウムで乾燥した。濾過により硫酸マグネシウムを除き、濃縮し残渣をシリカゲルカラムクロマトグラフィーにより精製し、目的物を4.0g(収率89%)得た。
1H−NMR(400MHz,CDCl3):δ2.79(s,3H),6.88(t,3H),7.01(d,1H),7.23(t,1H),7.26(s,1H),7.60(d,1H),11.81(s,1H)
4- (2-methoxyphenyl) -2-methylthiazole (4.82 g, 23.5 mmol) was dissolved in dehydrated dichloromethane (117 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1M dichloromethane solution, 26 ml, 25.8 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and allowed to react overnight. After the reaction, the reaction solution was ice-cooled, and quenched by adding an aqueous sodium hydrogen carbonate solution. The mixture was extracted with chloroform, and the organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 4.0 g (yield 89%) of the desired product.
1 H-NMR (400 MHz, CDCl 3 ): δ 2.79 (s, 3H), 6.88 (t, 3H), 7.01 (d, 1H), 7.23 (t, 1H), 7.26 (S, 1H), 7.60 (d, 1H), 11.81 (s, 1H)
ビス2−(2−メチルチアゾール−4−イル)フェノラト亜鉛(II) Bis 2- (2-methylthiazol-4-yl) phenolato zinc (II)
2−(2−メチルチアゾール−4−イル)フェノール(1.0g,5.2mmol)をメタノール(20ml)に溶解させ、酢酸亜鉛(II)(480mg,2.6mmol)を加え、70℃で終夜撹拌した。反応後析出固体を減圧濾過で回収、メタノールで洗浄し目的物を645mg(収率56%)得た。 2- (2-methylthiazol-4-yl) phenol (1.0 g, 5.2 mmol) was dissolved in methanol (20 ml), zinc (II) acetate (480 mg, 2.6 mmol) was added, and the mixture was kept at 70 ° C. overnight. Stir. After the reaction, the precipitated solid was collected by vacuum filtration and washed with methanol to obtain 645 mg (yield 56%) of the desired product.
(実施例6)2−(1−メチル−2−フェニル−1H−イミダゾール−4−イル)フェノラト亜鉛(II)
4−(2−メトキシフェニル)−2−フェニル−1H−イミダゾール
Example 6 2- (1-Methyl-2-phenyl-1H-imidazol-4-yl) phenolato zinc (II)
4- (2-methoxyphenyl) -2-phenyl-1H-imidazole
2−ブロモ−1−(2−メトキシフェニル)エタノン(7.0g,30.6mmol)とベンズアミジン塩酸塩(5.26g,33.6mmol)、炭酸水素ナトリウム(10.26g,122mmol)をTHF(150ml)と水(38ml)に溶解し、還流させながら加熱し24時間反応させた。反応後、クロロホルムを加え、有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。濾過により硫酸マグネシウムを除き、濃縮し残渣をシリカゲルカラムクロマトグラフィーにより精製し、目的物を5.2g(収率68%)得た。
1H−NMR(400MHz,CDCl3):δ3.36(s,3H),3.98(s,3H)7.04(d,1H),7.17(t,1H),7.47(t,1H),7.83(s,1H),8.28(d,1H)
2-Bromo-1- (2-methoxyphenyl) ethanone (7.0 g, 30.6 mmol), benzamidine hydrochloride (5.26 g, 33.6 mmol), sodium bicarbonate (10.26 g, 122 mmol) in THF (150 ml) ) And water (38 ml), heated under reflux and allowed to react for 24 hours. After the reaction, chloroform was added, and the organic layer was washed with saturated brine and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 5.2 g (yield 68%) of the desired product.
1 H-NMR (400 MHz, CDCl 3 ): δ 3.36 (s, 3H), 3.98 (s, 3H) 7.04 (d, 1H), 7.17 (t, 1H), 7.47 ( t, 1H), 7.83 (s, 1H), 8.28 (d, 1H)
2−(2−フェニル−1H−イミダゾール−4−イル)フェノール 2- (2-Phenyl-1H-imidazol-4-yl) phenol
4−(2−メトキシフェニル)−2−フェニル−1H−イミダゾール(4.3g,17.2mmol)を脱水ジクロロメタン(86ml)に溶解し、−78℃のドライアイス−アセトンバスで冷却した。そこに三臭化ホウ素(1Mジクロロメタン溶液,26ml,25.8mmol)を静かに滴下した。その後室温まで昇温し、終夜反応させた。反応後、反応液を氷冷し、炭酸水素ナトリウム水溶液を加えクエンチを行った。酢酸エチルで抽出し、有機層を飽和食塩水で洗浄後、硫酸マグネシウムで乾燥した。濾過により硫酸マグネシウムを除き、濃縮した。残渣にクロロホルム(50ml)とヘキサン(300ml)を加え、を加え、溶け残った固体を濾取し、目的物を3.2g(収率79%)得た。
1H−NMR(400MHz,DMSO−d6):δ3.84(s,3H),6.82−6.86(m,2H),7.09(t,1H),7.50−7.57(m,3H),7.68(dd,1H),7.69−7.67(m,2H),7.87(s,1H),11.87(s,1H)
4- (2-methoxyphenyl) -2-phenyl-1H-imidazole (4.3 g, 17.2 mmol) was dissolved in dehydrated dichloromethane (86 ml) and cooled in a dry ice-acetone bath at −78 ° C. Boron tribromide (1M dichloromethane solution, 26 ml, 25.8 mmol) was gently added dropwise thereto. Thereafter, the temperature was raised to room temperature and allowed to react overnight. After the reaction, the reaction solution was ice-cooled, and quenched by adding an aqueous sodium hydrogen carbonate solution. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over magnesium sulfate. Magnesium sulfate was removed by filtration and concentrated. Chloroform (50 ml) and hexane (300 ml) were added to the residue, and the solid that remained undissolved was collected by filtration to obtain 3.2 g (yield 79%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 3.84 (s, 3H), 6.82-6.86 (m, 2H), 7.09 (t, 1H), 7.50-7. 57 (m, 3H), 7.68 (dd, 1H), 7.69-7.67 (m, 2H), 7.87 (s, 1H), 11.87 (s, 1H)
2−(1−メチル−2−フェニル−1H−イミダゾール−4−イル)フェノラト亜鉛(II) 2- (1-Methyl-2-phenyl-1H-imidazol-4-yl) phenolato zinc (II)
2−(2−フェニル−1H−イミダゾール−4−イル)フェノール(0.37g,1.6mmol)、炭酸セシウム(0.51g,1.6mmol)を脱水DMF(8ml)に懸濁させ、ヨウ化メチル(0.2ml,3.1mmol)を加えた。室温で終夜反応させ、水を加え、酢酸エチルで抽出した。有機層を水、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。濾過により硫酸マグネシウムを除き、濾液を濃縮した。得られた白色固体(330mg)と酢酸亜鉛(II)(129mg,0.7mmol)をメタノールに溶解させ、ピペリジン(139μl,1.4mmol)をくわえて70℃で終夜撹拌した。反応後、析出固体を減圧濾過で回収、メタノールで洗浄し目的物を213mg(収率48%)得た。
1H−NMR(400MHz,DMSO−d6):δ3.64(s,3H),6.43(t,1H),6.56(d,1H),6.95(t,1H),7.08(t,2H),7.24(t,1H),7.31(dd,1H),7.36−7.38(m,2H)7.65(s,1H)
2- (2-Phenyl-1H-imidazol-4-yl) phenol (0.37 g, 1.6 mmol) and cesium carbonate (0.51 g, 1.6 mmol) were suspended in dehydrated DMF (8 ml) and iodinated. Methyl (0.2 ml, 3.1 mmol) was added. The mixture was reacted at room temperature overnight, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was concentrated. The obtained white solid (330 mg) and zinc (II) acetate (129 mg, 0.7 mmol) were dissolved in methanol, piperidine (139 μl, 1.4 mmol) was added, and the mixture was stirred at 70 ° C. overnight. After the reaction, the precipitated solid was collected by filtration under reduced pressure and washed with methanol to obtain 213 mg (yield 48%) of the desired product.
1 H-NMR (400 MHz, DMSO-d 6 ): δ 3.64 (s, 3H), 6.43 (t, 1H), 6.56 (d, 1H), 6.95 (t, 1H), 7 .08 (t, 2H), 7.24 (t, 1H), 7.31 (dd, 1H), 7.36-7.38 (m, 2H) 7.65 (s, 1H)
上記蛍光スペクトルの測定(蛍光発光波長の測定)結果から、実施例1〜6の有機金属錯体は、いずれも青色〜紫色の蛍光を好適に発することができることが分かった。 From the measurement results of the above fluorescence spectrum (measurement of fluorescence emission wavelength), it was found that all of the organometallic complexes of Examples 1 to 6 can suitably emit blue to violet fluorescence.
これらの測定結果から、実施例の有機金属錯体は、蛍光を利用する発光材料等として好適に用いることができる有機金属錯体であることが確認された。本発明の有機金属錯体は、実施例に記載の有機金属錯体と共通する構造的特徴を有するものであり、実施例に記載の有機金属錯体と同様の特性を有し、蛍光を利用する発光材料等として好適に用いることができる。 From these measurement results, it was confirmed that the organometallic complexes of the examples are organometallic complexes that can be suitably used as a light-emitting material utilizing fluorescence. The organometallic complex of the present invention has the same structural characteristics as the organometallic complexes described in the examples, and has the same characteristics as the organometallic complexes described in the examples, and a light emitting material utilizing fluorescence Etc. can be suitably used.
Claims (3)
ことを特徴とする請求項1に記載の有機金属錯体。 The organometallic complex according to claim 1, wherein the central metal atom M represents beryllium, magnesium, zinc, or aluminum.
ことを特徴とする請求項1又は2に記載の有機金属錯体。The organometallic complex according to claim 1 or 2, wherein
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