JP2008222635A - Metal complex compound, coloring matter and organic electroluminescent element - Google Patents
Metal complex compound, coloring matter and organic electroluminescent element Download PDFInfo
- Publication number
- JP2008222635A JP2008222635A JP2007063535A JP2007063535A JP2008222635A JP 2008222635 A JP2008222635 A JP 2008222635A JP 2007063535 A JP2007063535 A JP 2007063535A JP 2007063535 A JP2007063535 A JP 2007063535A JP 2008222635 A JP2008222635 A JP 2008222635A
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- Prior art keywords
- complex compound
- metal complex
- ring
- group
- layer
- Prior art date
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- -1 Metal complex compound Chemical class 0.000 title claims abstract description 105
- 238000004040 coloring Methods 0.000 title abstract description 5
- 239000012044 organic layer Substances 0.000 claims abstract description 43
- 125000003118 aryl group Chemical group 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 81
- 150000001875 compounds Chemical class 0.000 claims description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 238000004528 spin coating Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims 2
- 125000005594 diketone group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 38
- 239000007787 solid Substances 0.000 description 37
- 238000003786 synthesis reaction Methods 0.000 description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 30
- 238000002347 injection Methods 0.000 description 26
- 239000007924 injection Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 17
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 235000002597 Solanum melongena Nutrition 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- 229940093475 2-ethoxyethanol Drugs 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910052714 tellurium Inorganic materials 0.000 description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 5
- 125000003282 alkyl amino group Chemical group 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000003097 hole (electron) Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 125000004434 sulfur atom Chemical group 0.000 description 5
- MYHJEGAMYOQPMR-UHFFFAOYSA-N 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dione Chemical compound C(CCC)OC=1C=C(C=CC=1OCCCC)C(CC(=O)C1=CC(=C(C=C1)OCCCC)OCCCC)=O MYHJEGAMYOQPMR-UHFFFAOYSA-N 0.000 description 4
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 4
- PYWQACMPJZLKOQ-UHFFFAOYSA-N 1,3-tellurazole Chemical compound [Te]1C=CN=C1 PYWQACMPJZLKOQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 description 3
- NKULZYZHHWIWCP-UHFFFAOYSA-N 3,4-dibutoxybenzoic acid Chemical compound CCCCOC1=CC=C(C(O)=O)C=C1OCCCC NKULZYZHHWIWCP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- MSQCQINLJMEVNJ-UHFFFAOYSA-N 1-chloroisoquinoline Chemical compound C1=CC=C2C(Cl)=NC=CC2=C1 MSQCQINLJMEVNJ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- YNCYPMUJDDXIRH-UHFFFAOYSA-N benzo[b]thiophene-2-boronic acid Chemical compound C1=CC=C2SC(B(O)O)=CC2=C1 YNCYPMUJDDXIRH-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- KBPUBCVJHFXPOC-UHFFFAOYSA-N ethyl 3,4-dihydroxybenzoate Chemical compound CCOC(=O)C1=CC=C(O)C(O)=C1 KBPUBCVJHFXPOC-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical compound [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical compound Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
この発明は、新規な金属錯体化合物、該化合物からなる色素、および該化合物を用いて作製した有機電界発光素子に関する。
本発明の化合物は機能性色素、特に緑〜赤色系りん光性色素として有用である。
本発明の有機電界発光素子は、表示用照明、表示装置などに利用できる。
The present invention relates to a novel metal complex compound, a dye comprising the compound, and an organic electroluminescence device produced using the compound.
The compounds of the present invention are useful as functional dyes, particularly green to red phosphorescent dyes.
The organic electroluminescent element of the present invention can be used for display illumination, display devices, and the like.
有機電界発光(エレクトロルミネッセンス、EL)素子は携帯電話やデジタルカメラ等の小型ディスプレイとして実用化され、将来のフレキシブルディスプレイ実現に向けて大きな期待が寄せられている。有機EL素子では本来絶縁体である有機層に高電場を印加することによって高密度の電荷が有機薄膜中に注入されて動作する。外部から注入された電子とホールは薄膜中を移動し、蛍光やりん光性有機分子上である確率で再結合し、この再結合のエネルギーが有機分子を励起させ、光エネルギーを放出する。この光エネルギー放出は蛍光やりん光現象と同じであり、EL色は蛍光やりん光(フォトルミネッセンス、PL)の色と一致する。
この有機EL素子中には高密度の電荷と励起子とが共存した状態となり、従来の有機材料を用いた素子では考えられない非常に過酷な条件で使用される。そのため、有機EL素子に利用される材料には化学的・電気的耐久性が求められる。現在、実用化されている有機EL素子は、キャリア輸送層や発光層を蒸着法によって積層して製膜されることから、使用されるキャリア輸送材や発光材料には、優れたキャリア輸送能や発光効率の他に、製膜するための昇華性も必要となる。さらに、大画面の有機EL素子を実用化するためには、高価な大型の真空蒸着装置が必要となり、有機EL素子大画面の実用化の大きな妨げとなっている。
Organic electroluminescence (electroluminescence, EL) elements have been put into practical use as small displays such as mobile phones and digital cameras, and there are great expectations for the realization of flexible displays in the future. An organic EL element operates by applying a high electric field to an organic layer that is originally an insulator to inject a high-density charge into the organic thin film. Electrons and holes injected from the outside move in the thin film and recombine with a certain probability on the fluorescent or phosphorescent organic molecule, and the energy of this recombination excites the organic molecule and emits light energy. This light energy emission is the same as the fluorescence or phosphorescence phenomenon, and the EL color matches the color of fluorescence or phosphorescence (photoluminescence, PL).
In this organic EL element, high-density electric charges and excitons coexist, and the organic EL element is used under extremely severe conditions that cannot be considered with an element using a conventional organic material. Therefore, chemical and electrical durability is required for the material used for the organic EL element. Since organic EL devices that are currently in practical use are formed by laminating a carrier transport layer and a light emitting layer by vapor deposition, the carrier transport materials and light emitting materials used have excellent carrier transport capability and In addition to luminous efficiency, sublimation for film formation is also required. Furthermore, in order to put an organic EL element having a large screen into practical use, an expensive large-sized vacuum vapor deposition apparatus is required, which is a great hindrance to the practical application of an organic EL element large screen.
一方、容易に大面積の薄膜形成が可能な蛍光色素分散型高分子有機EL素子に関する研究は、使用できる蛍光色素が限られていたことから、報告例は少ない。高分子系有機EL素子は、低分子系に比べて物理的強度が高く、塗布によって簡便に素子を製膜できる利点もあり、製造コストの低減化が期待できる。とくに、蛍光色素分散型高分子有機EL素子は蛍光色素を均一分散したものであり低分子系キャリア輸送材料やドーパントなどを用いることができるのも一つの特徴である。また、発光色に関しても分散する色素の自由度が高いため、青から赤までの各色および白色まで実現できる。さらに、蒸着法により製膜される低分子型EL素子では耐久性に悪影響を与えるとされる結晶化の問題や、高精細大型パネルの製造プロセスの難しさなどは、高分子分散溶液を用いたインクジェット法、ロールツーロール法等の印刷プロセスを採用することによって克服できる利点がある。 On the other hand, studies on fluorescent dye-dispersed polymer organic EL devices that can easily form a thin film with a large area are limited in the number of fluorescent dyes that can be used. The polymer organic EL element has higher physical strength than the low molecular weight element, and has an advantage that the element can be easily formed by coating, and a reduction in production cost can be expected. In particular, the fluorescent dye-dispersed polymer organic EL device is one in which a fluorescent dye is uniformly dispersed and a low-molecular carrier transport material, a dopant, or the like can be used. Moreover, since the freedom degree of the pigment | dye to disperse | distributes regarding a luminescent color is also high, it can implement | achieve each color from blue to red, and white. In addition, polymer dispersions were used for low-molecular EL devices formed by vapor deposition, because of problems such as crystallization, which is considered to have an adverse effect on durability, and difficulties in the manufacturing process of high-definition large-sized panels. There is an advantage that can be overcome by adopting a printing process such as an inkjet method or a roll-to-roll method.
従来、金属錯体化合物、例えば、白金錯体化合物について種々の構造および発光色の錯体が知られているが、赤色に高輝度で発光し、更に堅牢性、溶解性などの優れた化合物は少ない。例えば、Inorg. Chem. Vol.41, pp.3055-3066 (2002)には、下記の構造を有する白金錯体化合物が報告されている。
上記構造の化合物の発光スペクトルのλmaxは、600 nmである。
The λ max of the emission spectrum of the compound having the above structure is 600 nm.
白金錯体化合物などの金属錯体化合物は、電子分野等において種々の機能的用途が開発され、その多様性、機能性などのより一層の拡大を求めて、常に新しい化合物の開発が求められている。本発明はかかる事情に鑑みなされたものであって、発光輝度が高く、堅牢で、且つ、溶解性の良好なりん光性色素であり、また、良好な昇華性、高い耐熱性が求められる有機EL用色素としても有用な新規化合物を提供することを目的とする。 Metal functional compounds such as platinum complex compounds have been developed for various functional uses in the electronic field and the like, and the development of new compounds is constantly required in order to further expand their diversity and functionality. The present invention has been made in view of such circumstances, and is a fluorescent pigment having high emission luminance, robustness, good solubility, and excellent sublimation and high heat resistance. An object is to provide a novel compound useful also as a coloring matter for EL.
本発明の目的は、
一般式:
[式中、
Mは、二価または三価の金属原子、
A1は、芳香環または複素環であり、
A2は、複素環であり、
R1およびR2は、同一または異なって、アルキル基またはアリール基であり、R1およびR2の少なくとも一方は、アリール基であり、
mおよびnは1または2であり、mとnの合計は金属原子の価数(2または3)である。]
で示される金属錯体化合物によって達成される。
The purpose of the present invention is to
General formula:
[Where:
M is a divalent or trivalent metal atom,
A 1 is an aromatic ring or a heterocyclic ring,
A 2 is a heterocycle,
R 1 and R 2 are the same or different and are an alkyl group or an aryl group, and at least one of R 1 and R 2 is an aryl group,
m and n are 1 or 2, and the sum of m and n is the valence (2 or 3) of the metal atom. ]
It is achieved by a metal complex compound represented by
本発明は、該金属錯体化合物からなるりん光性色素を提供する。
本発明は、対向する陽極と陰極の間に有機層を有する有機電界発光素子において、該有機層が金属錯体化合物を含有することを特徴とする有機電界発光素子をも提供する。
さらに、本発明は、スピンコート法を用いて、金属錯体化合物を含有する有機層を形成することを特徴とする、有機電界発光素子の製法を提供する。
The present invention provides a phosphorescent dye comprising the metal complex compound.
The present invention also provides an organic electroluminescence device having an organic layer between an anode and a cathode facing each other, wherein the organic layer contains a metal complex compound.
Furthermore, this invention provides the manufacturing method of an organic electroluminescent element characterized by forming the organic layer containing a metal complex compound using a spin coat method.
本発明の金属錯体化合物は、青色〜赤色、特に緑色〜赤色で高輝度で発光(りん光)し、更に堅牢性、溶解性、昇華性などに優れている。本発明の金属錯体化合物は、各種材料の着色剤として、又有機EL素子の色素としても優れた性能を有する機能性色素として有用である。 The metal complex compound of the present invention emits light (phosphorescence) from blue to red, particularly green to red, with high luminance, and is excellent in fastness, solubility, sublimation and the like. The metal complex compound of the present invention is useful as a colorant for various materials and as a functional dye having excellent performance as a dye for an organic EL device.
本発明の金属錯体化合物において、中心金属Mに、含窒素化合物およびジケトン化合物が配位子として配位している。
<中心金属>
中心金属Mは、二価または三価の金属原子である。Mの具体例は白金(Pt)、パラジウム(Pd)、イリジウム(Ir)、ロジウム(Rh)、ルテニウム(Ru)、オスミウム(Os)、金(Au)である。
Mは白金であることが特に好ましい。
従って、金属錯体化合物は、一般式(II):
[式中、
A1は、芳香環または複素環であり、
A2は、複素環であり、
R1およびR2は、同一または異なって、アルキル基またはアリール基であり、R1およびR2の少なくとも一方は、アリール基である。]
で示される金属錯体化合物であることが特に好ましい。白金錯体化合物は、赤色に高輝度で発光し、更に堅牢性、溶解性、昇華性などに優れている。
In the metal complex compound of the present invention, a nitrogen-containing compound and a diketone compound are coordinated to the central metal M as a ligand.
<Center metal>
The central metal M is a divalent or trivalent metal atom. Specific examples of M are platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os), and gold (Au).
M is particularly preferably platinum.
Therefore, the metal complex compound has the general formula (II):
[Where:
A 1 is an aromatic ring or a heterocyclic ring,
A 2 is a heterocycle,
R 1 and R 2 are the same or different and are an alkyl group or an aryl group, and at least one of R 1 and R 2 is an aryl group. ]
A metal complex compound represented by the formula is particularly preferred. The platinum complex compound emits red light with high luminance, and is excellent in fastness, solubility, sublimation and the like.
<含窒素化合物>
含窒素化合物は、式:
で示される。
<Nitrogen-containing compounds>
Nitrogen-containing compounds have the formula:
Indicated by
A1は、5員環または6員環である。5員環は2つの二重結合を有し、6員環は3つの二重結合を有することが好ましい。A1の環は、炭素原子のみからなってよく、あるいは少なくとも1つの他の原子(例えば、窒素原子、硫黄原子、酸素原子、セレン原子またはテルル原子)を有していてもよい。A1は、例えば、複素原子を有しない5員環および6員環、1つの窒素原子を有する5員環または6員環、1つの酸素原子を有する5員環または6員環、1つの硫黄原子を有する5員環または6員環、1つのセレン原子を有する5員環または6員環、1つのテルル原子を有する5員環または6員環、2つの窒素原子を有する5員環または6員環、3つの窒素原子を有する5員環または6員環、1つの窒素原子および1つの酸素原子を有する5員環または6員環、1つの窒素原子および1つの硫黄原子を有する5員環または6員環、1つの窒素原子および1つのセレン原子を有する5員環または6員環、1つの窒素原子および1つのテルル原子を有する5員環または6員環であってよい。 A 1 is a 5-membered ring or a 6-membered ring. The 5-membered ring preferably has 2 double bonds, and the 6-membered ring preferably has 3 double bonds. Ring A 1 may consist solely of carbon atoms, or at least one other atom (e.g., nitrogen atom, sulfur atom, oxygen atom, selenium atom or tellurium atom) may have. A 1 is, for example, a 5-membered ring and a 6-membered ring having no hetero atom, a 5-membered or 6-membered ring having one nitrogen atom, a 5-membered or 6-membered ring having one oxygen atom, and one sulfur. 5- or 6-membered ring having an atom, 5- or 6-membered ring having one selenium atom, 5- or 6-membered ring having one tellurium atom, or 5-membered ring having 6 nitrogen rings or 6 5-membered ring, 5- or 6-membered ring with 3 nitrogen atoms, 5- or 6-membered ring with 1 nitrogen atom and 1 oxygen atom, 5-membered ring with 1 nitrogen atom and 1 sulfur atom Alternatively, it may be a 6-membered ring, a 5-membered ring having 1 nitrogen atom and 1 selenium atom or a 6-membered ring having 1 nitrogen atom and 1 tellurium atom.
A1の具体例は、5員環としては、シクロペンタジエン、ピロール、ピラゾール、イミダゾール、トリアゾール、フラン、オキサゾール、チオフェン、チアゾール、セレノフェン、セレナゾール、テルロフェン、テルラゾール、6員環としては、ベンゼン、ピリジン、ピラジン、ピリミジン、ピリダジンおよびトリアジンである。 Specific examples of A 1 include cyclopentadiene, pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, selenophene, selenazole, tellurophene, tellurazole, as a 5-membered ring, benzene, pyridine, Pyrazine, pyrimidine, pyridazine and triazine.
含窒素化合物において、A2は、少なくとも1つの窒素原子を有する5員環または6員環である。5員環は2つの二重結合を有し、6員環は3つの二重結合を有することが好ましい。A2は、例えば、1つの窒素原子を有する5員環または6員環、2つの窒素原子を有する5員環または6員環、3つの窒素原子を有する5員環または6員環、1つの窒素原子および少なくとも1つの(好ましくは1つまたは2つの)酸素原子を有する5員環または6員環、1つの窒素原子および少なくとも1つの(好ましくは1つまたは2つの)硫黄原子を有する5員環または6員環、1つの窒素原子および少なくとも1つの(好ましくは1つまたは2つの)セレン原子を有する5員環または6員環、1つの窒素原子および少なくとも1つの(好ましくは1つまたは2つの)テルル原子を有する5員環または6員環であってよい。 In the nitrogen-containing compound, A 2 is a 5-membered or 6-membered ring having at least one nitrogen atom. The 5-membered ring preferably has 2 double bonds, and the 6-membered ring preferably has 3 double bonds. A 2 represents, for example, a 5-membered or 6-membered ring having one nitrogen atom, a 5-membered or 6-membered ring having 2 nitrogen atoms, a 5-membered or 6-membered ring having 3 nitrogen atoms, 1 5-membered ring having a nitrogen atom and at least one (preferably one or two) oxygen atom or a six-membered ring, one nitrogen atom and at least one (preferably one or two) sulfur atom 5- or 6-membered ring, one nitrogen atom and at least one (preferably one or two) ring or six-membered ring, one nitrogen atom and at least one (preferably one or two) selenium atom 5) or 6-membered rings having a tellurium atom.
A2の具体例は、5員環としては、ピロール、ピラゾール、イミダゾール、トリアゾール、フラン、オキサゾール、チオフェン、チアゾール、セレノフェン、セレナゾール、テルロフェン、テルラゾール、6員環としては、ピリジン、ピラジン、ピリミジン、ピリダジンおよびトリアジンである。 Specific examples of A 2 include pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, selenophene, selenazole, tellurophene, tellurazole as the 5-membered ring, and pyridine, pyrazine, pyrimidine, pyridazine as the 6-membered ring. And triazine.
A1およびA2は、置換基を有していても良く、および/または縮合環を形成していてもよい。置換基は、電子供与基または電子吸引基のいずれであってもよい。置換基の例は、アルキル基(炭素数1〜25)、アリール基(炭素数6〜25)、アミノ基、アルキルアミノ基(炭素数1〜25)、アルコキシ基(炭素数1〜25)、アリールオキシ基(炭素数6〜25)、アシル基(炭素数2〜25)、アルコキシカルボニル基(炭素数2〜25)、アルキルチオ基(炭素数1〜25)、スルホニル基、ヒドロキシ基、ハロゲン原子(特に、フッ素原子、塩素原子、臭素原子、ヨウ素原子)、ハロゲン化アルキル基(炭素数1〜25)(例えば、パーフルオロアルキル基)、ハロゲン化アリール基(炭素数6〜25)、シアノ基、ニトロ基、ヘテロ環基(環の原子数は例えば4〜25、特に4〜10)であってよい。置換基の数は、0であってもよく(すなわち、置換基を有しなくてもよく)、あるいは1〜10であってもよい。
縮合環における他の環は、炭素原子のみからなってよく、あるいは少なくとも1つの他の原子(例えば、窒素原子、酸素原子、硫黄原子、セレン原子またはテルル原子)を有していてもよい。縮合している他の環は、2つ以上の環であってよく、他の環の原子数は、例えば、4〜15、特に5〜10である。他の環の例は、シクロペンタジエン環、ベンゼン環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、フラン環、チオフェン環、ピロール環、セレノフェン環、テルロフェン環、イミダゾール環、ピラゾール環、トリアゾール環、オキサゾール環、チアゾール環、オキサジアゾール環、チアジアゾール環、セレナゾール環、テルラゾール環、オキサジン環、ジオキサン環、オキサチアン環、ジチアン環であってよい。縮合環は、置換基を有していてもよい。
A 1 and A 2 may have a substituent and / or may form a condensed ring. The substituent may be either an electron donating group or an electron withdrawing group. Examples of the substituent include an alkyl group (1 to 25 carbon atoms), an aryl group (6 to 25 carbon atoms), an amino group, an alkylamino group (1 to 25 carbon atoms), an alkoxy group (1 to 25 carbon atoms), Aryloxy group (6 to 25 carbon atoms), acyl group (2 to 25 carbon atoms), alkoxycarbonyl group (2 to 25 carbon atoms), alkylthio group (1 to 25 carbon atoms), sulfonyl group, hydroxy group, halogen atom (In particular, fluorine atom, chlorine atom, bromine atom, iodine atom), halogenated alkyl group (C1-25) (for example, perfluoroalkyl group), halogenated aryl group (C6-25), cyano group , A nitro group, and a heterocyclic group (the number of ring atoms is, for example, 4 to 25, particularly 4 to 10). The number of substituents may be 0 (that is, it may not have a substituent), or may be 1-10.
The other ring in the condensed ring may consist of only carbon atoms or may have at least one other atom (for example, nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom). The other ring condensed may be two or more rings, and the number of atoms of the other ring is, for example, 4 to 15, particularly 5 to 10. Examples of other rings are cyclopentadiene ring, benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, furan ring, thiophene ring, pyrrole ring, selenophene ring, tellurophen ring, imidazole ring, pyrazole ring, triazole ring, It may be an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, a selenazole ring, a tellurazole ring, an oxazine ring, a dioxane ring, an oxathian ring, or a dithian ring. The condensed ring may have a substituent.
mおよびnは、1または2である。Mが二価である場合に、mおよびnは1である。Mが三価である場合に、mおよびnの一方が1であり、他方が2であるが、mが2でありnが1であることが好ましい。 m and n are 1 or 2. M and n are 1 when M is divalent. When M is trivalent, one of m and n is 1 and the other is 2, but it is preferable that m is 2 and n is 1.
含窒素化合物の具体例は、次のとおりである。
[上記式中,Rnは、n個(例えば1〜5)の数の置換基R(それぞれのRは同一または異なる。)を表し、
R1、R2、R3およびR4は置換基である。]
Specific examples of the nitrogen-containing compound are as follows.
[In the above formula, Rn represents n (for example, 1 to 5) number of substituents R (each R is the same or different).
R 1 , R 2 , R 3 and R 4 are substituents. ]
<ジケトン化合物>
ジケトン化合物は、式:
で示される。
<Diketone compound>
The diketone compound has the formula:
Indicated by
ジケトン化合物において、R1およびR2は、アリール基またはアルキル基、好ましくはアリール基である。アリール基は、5員環または6員環であってよく、6員環であることが好ましい。アリール基は、環中に複素原子を有していてもよく、複素原子の例は、窒素原子、酸素原子、硫黄原子、セレン原子、テルル原子などである。アリール基の具体例は、シクロペンタジエニル基、フェニル基、ピロール基、ピリジン基、ピラゾール基、イミダゾール基、トリアゾール基、フラン基、オキサゾール基、オキサジアゾール基、チオフェン基、チアゾール基、セレノフェン基、セレナゾール基、テルロフェン基、テルラゾール基などである。
R1およびR2は、対称(特に、線対称)なジケトン化合物を形成するように、同様または鏡像体であることが好ましい。
In the diketone compound, R 1 and R 2 are an aryl group or an alkyl group, preferably an aryl group. The aryl group may be a 5-membered ring or a 6-membered ring, and is preferably a 6-membered ring. The aryl group may have a hetero atom in the ring, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and the like. Specific examples of the aryl group include cyclopentadienyl group, phenyl group, pyrrole group, pyridine group, pyrazole group, imidazole group, triazole group, furan group, oxazole group, oxadiazole group, thiophene group, thiazole group, and selenophene group. , A selenazole group, a tellurophen group, a tellurazole group, and the like.
R 1 and R 2 are preferably the same or enantiomers so as to form a symmetric (particularly line symmetric) diketone compound.
アリール基およびアルキル基は、置換基を有していてもよい。アリール基は環縮合していてもよい。置換基は、電子供与基または電子吸引基のいずれであってもよい。置換基の例は、アルキル基(炭素数1〜25)、アリール基(炭素数6〜25)、アミノ基、アルキルアミノ基(炭素数1〜25)、アルコキシ基(炭素数1〜25)、アリールオキシ基(炭素数6〜25)、アシル基(炭素数2〜25)、アルコキシカルボニル基(炭素数2〜25)、アルキルチオ基(炭素数1〜25)、スルホニル基、ヒドロキシ基、ハロゲン原子(特に、フッ素原子、塩素原子、臭素原子、ヨウ素原子)、ハロゲン化アルキル基(炭素数1〜25)(例えば、パーフルオロアルキル基)、ハロゲン化アリール基(炭素数6〜25)、シアノ基、ニトロ基、ヘテロ環基(環の原子数は例えば4〜25、特に4〜10)であってよい。置換基は、炭素数1〜15、例えば1〜12のアルコキシ基、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヘキシル基、オクチル基、デシル基、ドデシル基であることが特に好ましい。置換基の数は、0であってもよく(すなわち、置換基を有しなくてもよく)、あるいは1〜10、例えば2〜10であってもよい。R1およびR2における置換基の合計数が、2〜8、特に2〜6であることが好ましい。R1における置換基とR2における置換基の数が、同じで1〜3であることが好ましい。
環縮合しているアリール基であるR1およびR2の例は、ナフタレン基、アントラセン基、フェナントレン基、ピレン基、クリセン基、ペリレン基である。縮合環は、置換基を有していてもよい。
The aryl group and the alkyl group may have a substituent. The aryl group may be ring-fused. The substituent may be either an electron donating group or an electron withdrawing group. Examples of the substituent include an alkyl group (1 to 25 carbon atoms), an aryl group (6 to 25 carbon atoms), an amino group, an alkylamino group (1 to 25 carbon atoms), an alkoxy group (1 to 25 carbon atoms), Aryloxy group (6 to 25 carbon atoms), acyl group (2 to 25 carbon atoms), alkoxycarbonyl group (2 to 25 carbon atoms), alkylthio group (1 to 25 carbon atoms), sulfonyl group, hydroxy group, halogen atom (In particular, fluorine atom, chlorine atom, bromine atom, iodine atom), halogenated alkyl group (C1-25) (for example, perfluoroalkyl group), halogenated aryl group (C6-25), cyano group , A nitro group, and a heterocyclic group (the number of ring atoms is, for example, 4 to 25, particularly 4 to 10). The substituent is particularly preferably an alkoxy group having 1 to 15 carbon atoms, such as 1 to 12 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyl group, an octyl group, a decyl group or a dodecyl group. The number of substituents may be 0 (that is, it may not have a substituent), or 1 to 10, for example, 2 to 10. The total number of substituents in R 1 and R 2 is preferably 2 to 8, particularly 2 to 6. The number of substituents in R 1 and the number of substituents in R 2 is preferably the same and 1 to 3.
Examples of R 1 and R 2 which are ring-fused aryl groups are naphthalene group, anthracene group, phenanthrene group, pyrene group, chrysene group and perylene group. The condensed ring may have a substituent.
以下に、ジケトン化合物の具体例を例示する。主として対称な化合物を例示するが、非対称な化合物も可能である。
以下の化学式において、置換基ROは、アルコキシ基(炭素数1〜25)またはアリールオキシ基(炭素数6〜25)であることが好ましい。
アリール基が1つのアルコキシ基を有する化合物:
Below, the specific example of a diketone compound is illustrated. Although primarily symmetrical compounds are illustrated, asymmetric compounds are also possible.
In the following chemical formula, the substituent RO is preferably an alkoxy group (1 to 25 carbon atoms) or an aryloxy group (6 to 25 carbon atoms).
A compound in which an aryl group has one alkoxy group:
アリール基が2つのアルコキシ基を有する化合物:
A compound in which an aryl group has two alkoxy groups:
アリール基が3つのアルコキシ基を有する化合物:
A compound in which an aryl group has three alkoxy groups:
アリール基が1〜5個の置換基を有する化合物:
[式中、X、X1〜X5は、同じまたは異なって、例えば、アルキル基、ハロゲン原子、アミノ基、アルキルアミノ基、ジアルキルアミノ基、ニトロ基である。]
Compounds in which the aryl group has 1 to 5 substituents:
[Wherein, X and X 1 to X 5 are the same or different and are, for example, an alkyl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, or a nitro group. ]
アリール基が多環アリール基である化合物:
Compounds in which the aryl group is a polycyclic aryl group:
アリール基が複素環である化合物:
[式中、R1〜R8は、例えば、アルキル基、ハロゲン原子、アミノ基、アルキルアミノ基、ジアルキルアミノ基、ニトロ基である。]
Compounds in which the aryl group is a heterocycle:
[Wherein, R 1 to R 8 are, for example, an alkyl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, or a nitro group. ]
R1基とR2基が非対称である化合物:
[式中、Rは、ベンゼン環以外の基(例えば、アルキル基、複素環)、
X、X1〜X5は、同一または異なって、例えば、アルキル基、ハロゲン原子、アミノ基、アルキルアミノ基、ジアルキルアミノ基、ニトロ基である。]
Compounds in which R 1 group and R 2 group are asymmetric:
[Wherein, R represents a group other than a benzene ring (for example, an alkyl group, a heterocyclic ring),
X and X 1 to X 5 are the same or different and are, for example, an alkyl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, or a nitro group. ]
本発明の金属錯体化合物の特に好ましい具体例は、次のとおりである。
Particularly preferred specific examples of the metal complex compound of the present invention are as follows.
本発明の金属錯体化合物は、(i)金属塩と含窒素化合物を100〜200℃、好ましくは120〜150℃で、1〜48時間、好ましくは8〜24時間、加熱して前駆体を得る工程、次いで(ii)前駆体とジケトン化合物を70〜150℃、好ましくは90〜120℃で、1〜72時間、好ましくは10〜36時間加熱して金属錯体化合物を得る工程によって製造できる。ジケトン化合物を反応させた後に、含窒素化合物を反応させてもよい。反応において溶媒を存在させることが好ましい。 The metal complex compound of the present invention is obtained by heating (i) a metal salt and a nitrogen-containing compound at 100 to 200 ° C., preferably 120 to 150 ° C., for 1 to 48 hours, preferably 8 to 24 hours. It can be produced by a step, and (ii) a step of heating the precursor and diketone compound at 70 to 150 ° C., preferably 90 to 120 ° C., for 1 to 72 hours, preferably 10 to 36 hours to obtain a metal complex compound. After reacting the diketone compound, the nitrogen-containing compound may be reacted. It is preferred to have a solvent present in the reaction.
金属塩は、ハロゲン化金属であることが好ましい。ハロゲン化金属は、金属原子とハロゲン原子によって構成される。金属原子は、中心金属M(例えば、白金(Pt)、パラジウム(Pd)、イリジウム(Ir)、ロジウム(Rh)、ルテニウム(Ru)、オスミウム(Os)、金(Au))のみからなってもよいし、あるいは中心金属と他の金属との組合せであってもよい。他の金属の例は、アルカリ金属(例えば、リチウム、ナトリウム、カリウム、ルビジウム)、アルカリ土類金属(例えば、マグネシウム、カルシウム、ストロンチウム)などである。ハロゲン原子の例は、フッ素、塩素、臭素、ヨウ素である。
金属塩の具体例は、次のとおりである。
K2PtCl4、PtCl2、K2PdCl4、PdCl2、K3IrCl6、IrCl3、RhCl3、RuCl3、OsCl3、KAuCl4、
K2PtBr4、PtI2、K2PdI4、PdBr2、K3IrBr6、IrI3、RhBr3、RuBr3、OsBr3、KAuBr4
The metal salt is preferably a metal halide. The metal halide is composed of a metal atom and a halogen atom. The metal atom may be composed only of the central metal M (for example, platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os), gold (Au)). It may be a combination of the center metal and another metal. Examples of other metals are alkali metals (eg, lithium, sodium, potassium, rubidium), alkaline earth metals (eg, magnesium, calcium, strontium) and the like. Examples of halogen atoms are fluorine, chlorine, bromine and iodine.
Specific examples of the metal salt are as follows.
K 2 PtCl 4 , PtCl 2 , K 2 PdCl 4 , PdCl 2 , K 3 IrCl 6 , IrCl 3 , RhCl 3 , RuCl 3 , OsCl 3 , KAuCl 4 ,
K 2 PtBr 4 , PtI 2 , K 2 PdI 4 , PdBr 2 , K 3 IrBr 6 , IrI 3 , RhBr 3 , RuBr 3 , OsBr 3 , KAuBr 4
含窒素化合物およびジケトン化合物の量は、得ようとする金属錯体化合物における含窒素化合物とジケトン化合物の比に依存する。含窒素化合物の量は、金属塩1モルに対して、1〜8モル、例えば2〜5モルであってよい。ジケトン化合物の量は、前駆体1モルに対して1〜6モル、例えば1〜3モルであってよい。
溶媒は、工程(i)および(ii)に対して不活性であり、反応物を溶解し、反応に必要な温度を維持できるものであればどのような化合物であっても良い。溶媒の量は前駆体1ミリモルに対して5〜150mL、特に25〜75mLであることが好ましい。製造した金属錯体化合物は、固体として析出することなどにより容易に単離することができる。
金属錯体化合物を精製してもよい。精製には、抽出、再結晶、クロマトグラフィーなどを使用することができる。
The amount of the nitrogen-containing compound and the diketone compound depends on the ratio of the nitrogen-containing compound to the diketone compound in the metal complex compound to be obtained. The amount of the nitrogen-containing compound may be 1 to 8 mol, for example 2 to 5 mol, relative to 1 mol of the metal salt. The amount of the diketone compound may be 1 to 6 mol, for example 1 to 3 mol, relative to 1 mol of the precursor.
The solvent may be any compound as long as it is inert to the steps (i) and (ii) and can dissolve the reactant and maintain the temperature necessary for the reaction. The amount of the solvent is preferably 5 to 150 mL, particularly 25 to 75 mL, with respect to 1 mmol of the precursor. The produced metal complex compound can be easily isolated by depositing it as a solid.
The metal complex compound may be purified. For purification, extraction, recrystallization, chromatography and the like can be used.
本発明の金属錯体化合物は、色素、特にりん光性色素として使用できる。
本発明の金属錯体化合物は、溶媒、特に有機溶媒に容易に溶解するので、溶液塗布(特に、スピンコート)できる。金属錯体化合物の溶液を塗布(特に、スピンコート)した後に溶媒を除去することによって金属錯体化合物層を得ることができる。
The metal complex compound of the present invention can be used as a dye, particularly a phosphorescent dye.
Since the metal complex compound of the present invention is easily dissolved in a solvent, particularly an organic solvent, it can be applied by solution (in particular, spin coating). A metal complex compound layer can be obtained by applying a solution of a metal complex compound (particularly, spin coating) and then removing the solvent.
溶媒の例としては、脂肪族炭化水素、例えばペンタン、ヘキサン、ヘプタン;芳香族炭化水素、例えばベンゼン、トルエン、キシレン;脂環式炭化水素、例えばシクロヘキサン、メチルシクロヘキサン、デカリン;石油系溶媒、例えば石油エーテル、石油ベンジン;ハロゲン化炭化水素、四塩化炭素、クロロホルム、1,2−ジクロロエタン;エーテル、例えばエチルエーテル、イソプロピルエーテル、アニソール、ジオキサン、テトラヒドロフラン;ケトン、例えばアセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、アセトフェノン、イソフォロン;エステル、例えば酢酸エチル、酢酸ブチル;アミド、例えばジメチルフォルムアミド;アセトニトリル;ジメチルスルフォキシド;ハロゲン化ベンゼン、例えばクロロベンゼン、ジクロロベンゼンが挙げられる。 Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, heptane; aromatic hydrocarbons such as benzene, toluene, xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin; petroleum solvents such as petroleum Ethers, petroleum benzines; halogenated hydrocarbons, carbon tetrachloride, chloroform, 1,2-dichloroethane; ethers such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, Acetophenone, isophorone; esters such as ethyl acetate, butyl acetate; amides such as dimethylformamide; acetonitrile; dimethyl sulfoxide; Examples include lorobenzene and dichlorobenzene.
スピンコートによって、有機電界発光素子の有機層(例えば、ホール注入層、ホール輸送層、発光層、電子輸送層、電子注入層)を形成することができる。例えば、陰極、陽極、ホール(電子)輸送層、ホール(電子)注入層などの基材の上に有機層をスピンコートする。スピンコート操作において、100〜10000rpm、例えば500〜4000rpmで0.1〜30分間、例えば0.5〜3分間、基材を回転させることが好ましい。スピンコートする際に、溶液における固体(特に金属錯体化合物)の濃度は、0.0001〜10重量%、例えば、0.001〜1重量%であることが好ましい。スピンコートによって、厚さ5〜500nm、例えば25〜250nm(乾燥後の膜厚)の膜を形成する。スピンコートは、真空蒸着などに比較して、物質が蒸着時に飛散するという物質の無駄が生じることがなく、複雑な工程を必要とせず、製造コストが低く、簡便に行えるという利点がある。 The organic layer (for example, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer) of the organic electroluminescent element can be formed by spin coating. For example, an organic layer is spin-coated on a substrate such as a cathode, an anode, a hole (electron) transport layer, or a hole (electron) injection layer. In the spin coating operation, it is preferable to rotate the substrate at 100 to 10000 rpm, for example, 500 to 4000 rpm, for 0.1 to 30 minutes, for example, 0.5 to 3 minutes. In spin coating, the concentration of the solid (particularly the metal complex compound) in the solution is preferably 0.0001 to 10% by weight, for example, 0.001 to 1% by weight. A film having a thickness of 5 to 500 nm, for example, 25 to 250 nm (film thickness after drying) is formed by spin coating. Compared with vacuum deposition or the like, spin coating has the advantage that the material is not wasted when the material is deposited, and no complicated process is required, and the manufacturing cost is low and can be easily performed.
対向する陽極と陰極の間に有機層を有する有機電界発光素子において、該有機層が金属錯体化合物を含有する。
有機層の例は、発光層、ホール輸送層、電子輸送層、ホールブロック層、電子ブロック層、ホール注入層、電子注入層である。金属錯体化合物を含有する有機層は、発光層であることが好ましい。
本発明において、有機電界発光素子は、有機層に加えて、基板、陽極、陰極を有する。
In an organic electroluminescent device having an organic layer between an anode and a cathode facing each other, the organic layer contains a metal complex compound.
Examples of the organic layer are a light emitting layer, a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer. The organic layer containing the metal complex compound is preferably a light emitting layer.
In the present invention, the organic electroluminescent element has a substrate, an anode, and a cathode in addition to the organic layer.
次のような層構成を有することが好ましい。
(i)陽極/ホール注入層/ホール輸送層/発光層/電子輸送層/電子注入層/陰極
(ii)陽極/ホール注入層/ホール輸送層/発光層/電子注入輸送層/陰極
(iii)陽極/ホール注入輸送層/発光層/電子輸送層/電子注入層/陰極
(iv)陽極/ホール注入輸送層/発光層/電子注入輸送層/陰極
(v)陽極/ホール注入層/ホール輸送層/発光層/陰極
(vi)陽極/発光層/電子輸送層/電子注入層/陰極
(vii)陽極/ホール注入輸送層/発光層/陰極
(viii)陽極/発光層/電子注入輸送層/陰極
(ix)陽極/発光層/陰極
層構成において、ホールブロック層が陽極に隣接して存在してよく、電子ブロック層が陰極に隣接して存在してよい。
It is preferable to have the following layer structure.
(I) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (ii) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / cathode (iii) Anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (iv) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (v) anode / hole injection layer / hole transport layer / Light emitting layer / cathode (vi) anode / light emitting layer / electron transport layer / electron injection layer / cathode (vii) anode / hole injection transport layer / light emitting layer / cathode (viii) anode / light emitting layer / electron injection transport layer / cathode (Ix) Anode / light emitting layer / cathode In the layer configuration, the hole blocking layer may be present adjacent to the anode, and the electron blocking layer may be present adjacent to the cathode.
基板の上に陽極を形成してもよいし、あるいは基板の上に陰極を形成してもよい。
基板は、特に限定されないが、ジルコニア安定化イットリウム、ガラス等の無機材料;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルや、ポリエチレン、ポリカーボネート、ポリエーテルスルフォン、ポリアリレート、アリルジグリコールカーボネート、ポリイミド、ポリシクロオレフィン、ノルボルネン樹脂、ポリ(クロロトリフルオロエチレン)、ポリテトラフルオロエチレン、ポリテトラフルオロエチレン−ポリエチレン共重合体等の高分子材料であってよい。基板は、これらの2種以上の材料を組み合わせた複合シートであってもよい。さらに、基板に、例えば、カラーフィルタ膜、色変換膜、誘電体反射膜を組み合わせて、発光色をコントロールすることもできる。
An anode may be formed on the substrate, or a cathode may be formed on the substrate.
The substrate is not particularly limited, but inorganic materials such as zirconia-stabilized yttrium and glass; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyethylene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, It may be a polymer material such as polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), polytetrafluoroethylene, polytetrafluoroethylene-polyethylene copolymer. The substrate may be a composite sheet combining these two or more materials. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.
陽極に使用する物質としては、金属、合金、金属酸化物、導電性化合物、又はこれらの2種以上が挙げられる。具体例としては金、白金、銀、銅、コバルト、ニッケル、パラジウム、バナジウム、タングステン、酸化錫、酸化亜鉛、ITO(酸化インジウムスズ)、ポリチオフェン、ポリピロール等が挙げられる。陽極に使用する物質は、単独で使用しても良く、あるいは2種以上併用しても良い。陽極に使用する物質は、隣接する層との密着性やイオン化ポテンシャル、安定性等を考慮して選ばれる。 Examples of the substance used for the anode include metals, alloys, metal oxides, conductive compounds, or two or more of these. Specific examples include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, and polypyrrole. The substances used for the anode may be used alone or in combination of two or more. The material used for the anode is selected in consideration of adhesion to adjacent layers, ionization potential, stability, and the like.
陽極は、例えば、蒸着法、スパッタリング法等の方法により、基板の上に形成することができる。また、陽極は一層構造であっても良く、あるいは多層構造であっても良い。陽極のシート電気抵抗は、数百Ω/□以下、より好ましくは、5〜50Ω/□程度であることが好ましい。陽極の厚さは、一般に、5〜1000nm程度、より好ましくは、10〜500nm程度である。 The anode can be formed on the substrate by a method such as vapor deposition or sputtering. Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably several hundred Ω / □ or less, more preferably about 5 to 50 Ω / □. The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm.
陰極に使用する物質としては金属、合金、金属酸化物、導電性化合物、又はこれらの2種以上が挙げられる。具体例としてはアルカリ金属(例えばLi、Na、K、Cs等)又はフッ化アルカリ金属、ナフトール等の有機塩、アルカリ土類金属(例えばMg、Ca等)又はフッ化アルカリ土類金属、金、銀、白金、鉛、アルミニウム、ナトリウム−カリウム合金、リチウム−アルミニウム合金、マグネシウム−銀合金、又はそれらの2種以上を併用する合金、インジウム、イッテルビウム等の希土類金属が挙げられる。陰極に使用する物質は、電子注入輸送の機能を有する層、陰極と隣接する層との密着性や、イオン化ポテンシャル、安定性等を考慮して選ばれる。 Examples of the substance used for the cathode include metals, alloys, metal oxides, conductive compounds, or two or more of these. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.) or alkali metal fluorides, organic salts such as naphthol, alkaline earth metals (eg, Mg, Ca, etc.) or alkali earth fluoride metals, gold, Examples thereof include silver, platinum, lead, aluminum, a sodium-potassium alloy, a lithium-aluminum alloy, a magnesium-silver alloy, or an alloy using two or more of these in combination, and rare earth metals such as indium and ytterbium. The substance used for the cathode is selected in consideration of the layer having the function of electron injection and transport, the adhesion between the cathode and the adjacent layer, the ionization potential, the stability, and the like.
陰極の作製には電子ビーム法、スパッタリング法、抵抗加熱蒸着法、コーティング法等の方法が用いられ、金属を単体で蒸着することも、二成分以上を同時に蒸着することもできる。さらに、2種以上の金属を同時に蒸着して合金電極を形成することも可能である。また、あらかじめ調製した合金を蒸着させても良い。陰極のシート抵抗は低い方が好ましく、数百Ω/□以下がより好ましい。
陰極の厚さは、使用する物質により適宜選択可能であるが、通常10nm〜5μmの範囲が好ましく、より好ましくは50nm〜1μmであり、さらに好ましくは100nm〜1μmである。
A method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, or a coating method is used for producing the cathode, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, it is also possible to form an alloy electrode by simultaneously depositing two or more kinds of metals. Further, an alloy prepared in advance may be deposited. The sheet resistance of the cathode is preferably low, and more preferably several hundred Ω / □ or less.
Although the thickness of a cathode can be suitably selected according to the substance to be used, the range of 10 nm-5 micrometers is preferable normally, More preferably, it is 50 nm-1 micrometer, More preferably, it is 100 nm-1 micrometer.
本発明の金属錯体化合物を、有機層、特に、ホール注入/ホール輸送/発光/電子輸送/電子注入の少なくとも1つの機能を有する層において使用する。
本発明の金属錯体化合物は、ホール注入輸送機能、発光機能および電子注入輸送機能のいずれか1つを有する。
The metal complex compound of the present invention is used in an organic layer, particularly a layer having at least one function of hole injection / hole transport / light emission / electron transport / electron injection.
The metal complex compound of the present invention has any one of a hole injection transport function, a light emission function, and an electron injection transport function.
ホール注入輸送機能を持つ化合物を、ホール注入層、ホール輸送層、ホール注入輸送層等のホール注入輸送機能を有する層において使用する。
ホール注入輸送機能を有する層において、本発明の金属錯体化合物のみ、他の化合物のみ、あるいは金属錯体化合物と他の化合物との組合せを使用する。
ホール注入輸送機能を有する他の化合物の具体例としては、フタロシアニン誘導体、トリアリールメタン誘導体、トリアリールアミン誘導体、オキサゾール誘導体、ヒドラゾン誘導体、スチルベン誘導体、ピラゾリン誘導体、ポリシラン誘導体、ポリフェニレンビニレン及びその誘導体、ポリチオフェン及びその誘導体、ポリ−N−ビニルカルバゾール誘導体等が挙げられる。ホール注入輸送機能を有する他の化合物は、単独で使用しても良く、あるいは2種以上併用しても良い。
A compound having a hole injection transport function is used in a layer having a hole injection transport function, such as a hole injection layer, a hole transport layer, and a hole injection transport layer.
In the layer having a hole injecting and transporting function, only the metal complex compound of the present invention, only another compound, or a combination of the metal complex compound and another compound is used.
Specific examples of other compounds having a hole injecting and transporting function include phthalocyanine derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof, polythiophene And derivatives thereof, poly-N-vinylcarbazole derivatives, and the like. Other compounds having a hole injecting and transporting function may be used alone or in combination of two or more.
発光機能を有する化合物を、発光層において使用する。発光層において、本発明の金属錯体化合物のみ、他の化合物のみ、あるいは金属錯体化合物と他の化合物との組合せを使用する。
本発明の金属錯体化合物以外の発光機能を有する化合物としては、例えば、アクリドン誘導体、キナクリドン誘導体、ジケトピロロピロール誘導体、多環芳香族化合物、トリアリールアミン誘導体、エナミン構造を有する化合物、有機金属錯体、スチルベン誘導体、ピラン誘導体、オキサゾン誘導体、ベンゾチアゾール誘導体、ベンゾオキサゾール誘導体、ベンゾイミダゾール誘導体、ピラジン誘導体、ケイ皮酸エステル誘導体、ポリ−N−ビニルカルバゾール及びその誘導体、ポリチオフェン及びその誘導体、ポリフェニレン及びその誘導体、ポリフルオレン及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリビフェニレンビニレン及びその誘導体、ポリターフェニレンビニレン及びその誘導体、ポリナフチレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体等が挙げられる。これら発光機能を有する化合物は単独で使用しても良く、あるいは2種以上併用しても良い。
A compound having a light emitting function is used in the light emitting layer. In the light emitting layer, only the metal complex compound of the present invention, only another compound, or a combination of the metal complex compound and another compound is used.
Examples of the compound having a light emitting function other than the metal complex compound of the present invention include an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound, a triarylamine derivative, a compound having an enamine structure, and an organometallic complex , Stilbene derivatives, pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof Polyfluorene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polybiphenylene vinylene and derivatives thereof, polyterphenylene vinylene and derivatives thereof, polynaphthylene vinylene and Derivatives, polythienylenevinylene and a derivative thereof. These compounds having a light emitting function may be used alone or in combination of two or more.
上記の多環芳香族化合物としては、例えば、ルブレン、アントラセン、テトラセン、ピレン、ペリレン、クリセン、デカシクレン、コロネン、テトラフェニルシクロペンタジエン、ペンタフェニルシクロペンタジエン、9,10−ジフェニルアントラセン、9,10−ビス(フェニルエチニル)アントラセン、1,4−ビス(9'−エチニルアントラセニル)ベンゼン、4,4'−ビス(9"−エチニルアントラセニル)ビフェニル等が挙げられる。
本発明の金属錯体化合物を含有している有機層は、発光層であることが好ましい。
Examples of the polycyclic aromatic compound include rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, and 9,10-bis. (Phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl and the like can be mentioned.
The organic layer containing the metal complex compound of the present invention is preferably a light emitting layer.
電子注入輸送機能を有する化合物を、電子注入層、電子輸送層、電子注入輸送層等の電子注入輸送機能を有する層において使用する。
電子注入輸送機能を有する層において、本発明の金属錯体化合物のみ、他の化合物のみ、あるいは金属錯体化合物と他の化合物との組合せを使用する。
電子注入輸送機能を有する他の化合物としては、例えば、有機金属錯体、オキサジアゾール誘導体、トリアゾール誘導体、トリアジン誘導体、ペリレン誘導体、キノリン誘導体、ジフェニルキノン誘導体、ニトロ置換フルオレノン誘導体、チオピランジオキサイド誘導体、キノキサリン誘導体、ベンゾイミダゾール誘導体等が挙げられる。
A compound having an electron injecting and transporting function is used in a layer having an electron injecting and transporting function such as an electron injecting layer, an electron transporting layer, and an electron injecting and transporting layer.
In the layer having an electron injecting and transporting function, only the metal complex compound of the present invention, only another compound, or a combination of the metal complex compound and another compound is used.
Examples of other compounds having an electron injecting and transporting function include, for example, organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives, Examples thereof include quinoxaline derivatives and benzimidazole derivatives.
本発明の有機電界発光素子においては、有機層が金属錯体化合物を含有している。他の化合物(例えば、発光機能またはホール(電子)注入輸送機能を有する他の化合物)を併用する場合、有機層中に占める金属錯体化合物の割合は、好ましくは0.001重量%以上、より好ましくは0.1〜99.9重量%、例えば1〜99重量%、特に2〜30重量%、特別に1〜10重量%である。
有機層においては、本発明の金属錯体化合物以外の、上記のような(発光機能またはホール(電子)注入輸送機能を有する)他の化合物を使用してよい。他の化合物の量は、有機層に対して、0.01〜90重量%、例えば0.1〜50重量%、特に1〜30重量%であってよい。
In the organic electroluminescent element of the present invention, the organic layer contains a metal complex compound. When other compounds (for example, other compounds having a light emitting function or a hole (electron) injecting and transporting function) are used in combination, the proportion of the metal complex compound in the organic layer is preferably 0.001% by weight or more, more preferably Is 0.1 to 99.9% by weight, for example 1 to 99% by weight, in particular 2 to 30% by weight, in particular 1 to 10% by weight.
In the organic layer, other compounds (having a light emitting function or a hole (electron) injecting and transporting function) as described above other than the metal complex compound of the present invention may be used. The amount of other compounds may be from 0.01 to 90% by weight, for example from 0.1 to 50% by weight, in particular from 1 to 30% by weight, based on the organic layer.
溶液塗布法により有機層(特に、発光層)を形成する場合、発光機能またはホール(電子)注入輸送機能を有する化合物のみ、あるいはこれら化合物とバインダーポリマーとを溶媒に溶解又は分散させて塗布液とする。バインダーポリマーとしては、例えば、ポリ−N−ビニルカルバゾール、ポリアリレート、ポリスチレン、ポリエステル、ポリシロキサン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリエーテル、ポリカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリパラキシレン、ポリエチレン、ポリエチレンエーテル、ポリプロピレンエーテル、ポリフェニレンオキサイド、ポリエーテルスルフォン、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリフェニレンエチニレン及びその誘導体、ポリフルオレン及びその誘導体、ポリチエニレンビニレン及びその誘導体等の高分子化合物が挙げられる。バインダーポリマーは、単独で使用しても良く、あるいは2種以上併用しても良い。バインダーポリマーの量は、有機層の1〜99重量%、例えば10〜80重量%であってよい。 When an organic layer (especially, a light emitting layer) is formed by a solution coating method, only a compound having a light emitting function or a hole (electron) injecting and transporting function, or by dissolving or dispersing these compounds and a binder polymer in a solvent, To do. Examples of the binder polymer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyethylene ether, polypropylene ether, polyphenylene oxide, polyether sulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyphenylene ethynylene and derivatives thereof, polyfluorene and derivatives thereof, polythienylene vinylene and derivatives thereof, etc. The high molecular compound of these is mentioned. The binder polymer may be used alone or in combination of two or more. The amount of binder polymer may be 1-99% by weight of the organic layer, for example 10-80% by weight.
有機層(例えば、ホール注入輸送機能を有する層、発光層、電子注入輸送機能を有する層)の形成方法に関しては、特に限定するものではなく、真空蒸着法、イオン化蒸着法、溶液塗布法(例えば、スピンコート法、キャスト法、ディップコート法、バーコート法、ロールコート法、ラングミュア・ブロゼット法、インクジェット法等)により薄膜を形成することにより作製することができる。本発明においては、有機層の形成は、スピンコート法を用いることが好ましい。
本発明の金属錯体化合物は、溶剤に対して高い溶解性を有しており、均一な分散状態で溶剤に良好に溶解するので、溶液塗布(特に、スピンコート)により、良好な有機層が得られる。
各有機層の厚さは、好ましくは5〜500nm、例えば25〜250nm、特に50〜150nmであってよい。
The formation method of the organic layer (for example, a layer having a hole injecting and transporting function, a light emitting layer, and a layer having an electron injecting and transporting function) is not particularly limited. , Spin coating method, casting method, dip coating method, bar coating method, roll coating method, Langmuir-brozzet method, ink jet method, and the like). In the present invention, the organic layer is preferably formed by a spin coating method.
Since the metal complex compound of the present invention has high solubility in a solvent and dissolves well in a solvent in a uniform dispersion state, a good organic layer can be obtained by solution coating (particularly, spin coating). It is done.
The thickness of each organic layer is preferably 5 to 500 nm, for example 25 to 250 nm, in particular 50 to 150 nm.
有機電界発光素子において、保護液、保護層(封止層)を設けても良い。これにより、有機電界発光素子が酸素や水分等と接触することが防止される。保護液は、例えば、パラフィン、流動パラフィン、シリコーンオイル、フルオロカーボン油、ゼオライト含有フルオロカーボン油等の不活性液体であってよい。保護層は、例えば、有機高分子材料(例えば、光硬化性樹脂)、無機材料であってよい。
有機電界発光素子に印加する電圧は、例えば、0.1〜50Vである。
In the organic electroluminescent element, a protective liquid and a protective layer (sealing layer) may be provided. This prevents the organic electroluminescent element from coming into contact with oxygen or moisture. The protective liquid may be an inert liquid such as paraffin, liquid paraffin, silicone oil, fluorocarbon oil, or zeolite-containing fluorocarbon oil. The protective layer may be, for example, an organic polymer material (for example, a photocurable resin) or an inorganic material.
The voltage applied to the organic electroluminescent element is, for example, 0.1 to 50V.
本発明の有機電界発光素子は、表示素子、ディスプレイ、バックライト、電子写真、照明光源、記録光源、露光光源、読み取り光源、標識、看板、インテリア、光通信等に好適に利用できる。 The organic electroluminescence device of the present invention can be suitably used for display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.
以下に実施例を挙げて本発明を具体的に説明するが、本発明は、以下の実施例に制約されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
(1)ジケトン化合物(1,3-ビス(3,4-ジブトキシフェニル)プロパン-1,3-ジオン)の合成(1) Synthesis of diketone compound (1,3-bis (3,4-dibutoxyphenyl) propane-1,3-dione)
合成例1
3,4-ジブトキシ安息香酸エチルの合成
Synthesis example 1
Synthesis of ethyl 3,4-dibutoxybenzoate
3,4-ジヒドロキシ安息香酸エチル(8.71 g, 47.8 mmol)、1-ヨードブタン(20.2 g, 110 mmol)および乾燥させた炭酸カリウム(27.5 g, 200 mmol)を500 mLの二口ナスフラスコに入れ、そこへ2-ブタノン225 mL を加えた後、窒素雰囲気下で3日間加熱還流させた。放冷後、固体を濾過によって除去し、ロータリーエバポレーターを用いて濾液の溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって3,4-ジブトキシ安息香酸エチルを白色固体として得た(13.1 g, 44.5 mmol, 93%)。 Ethyl 3,4-dihydroxybenzoate (8.71 g, 47.8 mmol), 1-iodobutane (20.2 g, 110 mmol) and dried potassium carbonate (27.5 g, 200 mmol) were placed in a 500 mL two-necked eggplant flask, 2-Butanone (225 mL) was added thereto, and the mixture was heated to reflux for 3 days under a nitrogen atmosphere. After allowing to cool, the solid was removed by filtration, and the solvent of the filtrate was distilled off using a rotary evaporator. The residue was purified by silica gel column chromatography (developing solvent; chloroform) to give ethyl 3,4-dibutoxybenzoate as a white solid (13.1 g, 44.5 mmol, 93%).
1H NMR (CDCl3) δ(ppm): 0.99 (t, J = 7.1 Hz, 6H), 1.38 (t, J = 7.1 Hz, 3H), 1.46-1.56 (m, 4H), 1.78-1.86 (m, 4H), 4.05 (t, J = 7.1 Hz, 4H), 4.34 (q, J = 7.1 Hz, 2H), 6.86 (d, J = 8.5 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.64 (dd, J = 2.0 Hz and 8.5 Hz, 1H).
MALDI-TOF MS: m/z 295 ([M + H]+).
Anal. Calcd for C17H26O4: C, 69.36; H, 8.90. Found: C, 69.02; H, 9.15.
1 H NMR (CDCl 3 ) δ (ppm): 0.99 (t, J = 7.1 Hz, 6H), 1.38 (t, J = 7.1 Hz, 3H), 1.46-1.56 (m, 4H), 1.78-1.86 (m , 4H), 4.05 (t, J = 7.1 Hz, 4H), 4.34 (q, J = 7.1 Hz, 2H), 6.86 (d, J = 8.5 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H ), 7.64 (dd, J = 2.0 Hz and 8.5 Hz, 1H).
MALDI-TOF MS: m / z 295 ([M + H] + ).
Anal. Calcd for C 17 H 26 O 4 : C, 69.36; H, 8.90. Found: C, 69.02; H, 9.15.
合成例2
3,4-ジブトキシ安息香酸の合成
Synthesis example 2
Synthesis of 3,4-dibutoxybenzoic acid
3,4-ジブトキシ安息香酸エチル(13.1 g, 44.5 mmol)および水酸化カリウム(12.0 g, 214 mmol)を 1 Lの四つ口ナスフラスコに入れ、そこへエタノール(330 mL)および水(220 mL)を加えた後、3時間加熱還流させた。放冷後、ロータリーエバポレーターにてエタノールを留去した後、1.0 M の塩酸を用いて酸性(pH = ca. 3)にし、析出した3,4-ジブトキシ安息香酸の白色固体を濾過によって集めた(11.17 g, 42.0 mmol, 95%)。 Ethyl 3,4-dibutoxybenzoate (13.1 g, 44.5 mmol) and potassium hydroxide (12.0 g, 214 mmol) were placed in a 1 L four-necked eggplant flask to which ethanol (330 mL) and water (220 mL) were added. ) Was added, and the mixture was heated to reflux for 3 hours. After standing to cool, ethanol was distilled off on a rotary evaporator, acidified with 1.0 M hydrochloric acid (pH = ca. 3), and the precipitated white solid of 3,4-dibutoxybenzoic acid was collected by filtration ( 11.17 g, 42.0 mmol, 95%).
1H NMR (CDCl3) δ (ppm): 0.99 (t, J = 7.1 Hz, 6H), 1.47-1.56 (m, 4H), 1.79-1.88 (m, 4H), 4.06 (t, J = 7.1 Hz, 2H), 4.08 (t, J = 7.1 Hz, 2H),6.89 (d, J = 8.5 Hz, 1H), 7.59 (d, J =2.0 Hz, 1H), 7.72 (dd, J = 2.0 Hz and 8.5 Hz, 1H)
MALDI-TOF MS: m/z 267 ([M + H]+)
Anal. Calcd for C15H22O4: C, 67.64; H, 8.33. Found: C, 67.58; H, 8.58.
1 H NMR (CDCl 3 ) δ (ppm): 0.99 (t, J = 7.1 Hz, 6H), 1.47-1.56 (m, 4H), 1.79-1.88 (m, 4H), 4.06 (t, J = 7.1 Hz , 2H), 4.08 (t, J = 7.1 Hz, 2H), 6.89 (d, J = 8.5 Hz, 1H), 7.59 (d, J = 2.0 Hz, 1H), 7.72 (dd, J = 2.0 Hz and 8.5 Hz, 1H)
MALDI-TOF MS: m / z 267 ([M + H] + )
Anal. Calcd for C 15 H 22 O 4 : C, 67.64; H, 8.33. Found: C, 67.58; H, 8.58.
合成例3
3,4−ジブトキシアセトフェノンの合成
Synthesis example 3
Synthesis of 3,4-dibutoxyacetophenone
3,4-ジブトキシ安息香酸(5.61 g, 21.1 mmol)を 500 mLの三口ナスフラスコに入れ、乾燥テトラヒドロフラン 150 mLを加えた後、窒素雰囲気下に置換した。そこへメチルリチウムのジエチルエーテル溶液(1.6 mol/L, 40 mL)を1時間かけて滴下し、室温下にて14時間攪拌した。その後、 5.0 M の塩酸(150 mL)を1時間かけて滴下し、さらに1時間攪拌した。攪拌を止め、ロータリーエバポレーターにてテトラヒドロフランおよびジエチルエーテルを留去した。残った混合物にクロロホルム(150 mL)を加えて分液漏斗中で強く振とうし、水相を取り除いた。有機相を水(2 × 150 mL)および飽和食塩水(150 ml)で洗浄し、無水硫酸マグネシウムで乾燥させた後、ロータリーエバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって3,4−ジブトキシアセトフェノンを白色固体として得た(5.13 g, 19.4 mmol, 92%)。 3,4-Dibutoxybenzoic acid (5.61 g, 21.1 mmol) was placed in a 500 mL three-necked eggplant flask, 150 mL of dry tetrahydrofuran was added, and the atmosphere was replaced under a nitrogen atmosphere. Thereto was added methyl lithium in diethyl ether (1.6 mol / L, 40 mL) dropwise over 1 hour, and the mixture was stirred at room temperature for 14 hours. Thereafter, 5.0 M hydrochloric acid (150 mL) was added dropwise over 1 hour, and the mixture was further stirred for 1 hour. Stirring was stopped and tetrahydrofuran and diethyl ether were distilled off with a rotary evaporator. Chloroform (150 mL) was added to the remaining mixture and shaken vigorously in a separatory funnel to remove the aqueous phase. The organic phase was washed with water (2 × 150 mL) and saturated brine (150 ml), dried over anhydrous magnesium sulfate, and then the solvent was distilled off with a rotary evaporator. The residue was purified by silica gel column chromatography (developing solvent; chloroform) to give 3,4-dibutoxyacetophenone as a white solid (5.13 g, 19.4 mmol, 92%).
1H NMR (CDCl3) δ (ppm): 0.98 (t, J = 7.1 Hz, 3H), 0.99 (t, J = 7.1 Hz, 3H), 1.46-1.56 (m, 4H), 1.78-1.87 (m, 4H), 2.55 (s, 3H), 4.06 (t, J = 7.1 Hz, 2H), 4.07 (t, J = 7.1 Hz, 2H), 6.87 (d, J = 8.2 Hz, 1H) 7.51 (d, J =2.0 Hz, 1H), 7.54 (dd, J = 2.0 Hz and 8.2 Hz, 1H)
MALDI-TOF MS: m/z 265 ([M + H]+)
Anal. Calcd for C16H24O3: C, 72.69; H, 9.15. Found: C, 72.80; H, 9.46.
1 H NMR (CDCl 3 ) δ (ppm): 0.98 (t, J = 7.1 Hz, 3H), 0.99 (t, J = 7.1 Hz, 3H), 1.46-1.56 (m, 4H), 1.78-1.87 (m , 4H), 2.55 (s, 3H), 4.06 (t, J = 7.1 Hz, 2H), 4.07 (t, J = 7.1 Hz, 2H), 6.87 (d, J = 8.2 Hz, 1H) 7.51 (d, J = 2.0 Hz, 1H), 7.54 (dd, J = 2.0 Hz and 8.2 Hz, 1H)
MALDI-TOF MS: m / z 265 ([M + H] + )
Anal. Calcd for C 16 H 24 O 3 : C, 72.69; H, 9.15. Found: C, 72.80; H, 9.46.
合成例4
1,3-ビス(3,4-ジブトキシフェニル)プロパン-1,3-ジオンの合成
Synthesis example 4
Synthesis of 1,3-bis (3,4-dibutoxyphenyl) propane-1,3-dione
3,4-ジブトキシ安息香酸エチル(1.60 g, 5.44 mmol)および水素化ナトリウム(60 wt%で油中に分散させたもの, 578 mg, 1.44 mmol)を 50 mLの三口ナスフラスコに入れ窒素雰囲気下に置換した。そこへ乾燥テトラヒドロフラン6 mLを加え、60℃に保ちながら攪拌した。3,4-ジブトキシアセトフェノンの乾燥テトラヒドロフラン溶液(1.92 M, 2.6 mL)を30 分間かけて滴下し、溶液全量の約2/3を滴下したところでメタノール 0.01 mLを加え、その後、3,4-ジブトキシアセトフェノン溶液の残り全てを滴下して53時間加熱還流させた。常温まで放冷後、水50 mLを滴下し、1.0 M の塩酸で酸性にした。そこへクロロホルム(30 mL)を加え、混合物を分液漏斗に移し、強く振とうした後に有機層を分取した。さらに水層をクロロホルム(30 mL×2)で抽出した。全ての有機層を混合し、水(30 mL×2)および飽和食塩水(30 mL)で洗浄後、無水硫酸マグネシウムで乾燥させた。固体をろ過にて除去した後、ロータリーエバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で単離した後、メタノールから再結晶し、淡黄色固体として1,3-ビス(3,4-ジブトキシフェニル)プロパン-1,3-ジオンを得た(1.34 g, 2.61 mmol, 52%)。 Ethyl 3,4-dibutoxybenzoate (1.60 g, 5.44 mmol) and sodium hydride (60 wt% dispersed in oil, 578 mg, 1.44 mmol) were placed in a 50 mL three-necked eggplant flask under nitrogen atmosphere Replaced with Thereto was added 6 mL of dry tetrahydrofuran, and the mixture was stirred while maintaining at 60 ° C. A solution of 3,4-dibutoxyacetophenone in dry tetrahydrofuran (1.92 M, 2.6 mL) was added dropwise over 30 minutes. When about 2/3 of the total solution was added dropwise, 0.01 mL of methanol was added. All the remaining butoxyacetophenone solution was added dropwise and heated to reflux for 53 hours. After allowing to cool to room temperature, 50 mL of water was added dropwise and acidified with 1.0 M hydrochloric acid. Chloroform (30 mL) was added thereto, the mixture was transferred to a separatory funnel, and after shaking vigorously, the organic layer was separated. Further, the aqueous layer was extracted with chloroform (30 mL × 2). All organic layers were mixed, washed with water (30 mL × 2) and saturated brine (30 mL), and then dried over anhydrous magnesium sulfate. After removing the solid by filtration, the solvent was distilled off with a rotary evaporator. The residue was isolated by silica gel column chromatography (developing solvent; chloroform) and recrystallized from methanol to give 1,3-bis (3,4-dibutoxyphenyl) propane-1,3-dione as a pale yellow solid. Obtained (1.34 g, 2.61 mmol, 52%).
1H NMR (CDCl3) δ (ppm): 0.99 (t, J = 7.3 Hz, 12H), 1.46-1.59 (m, 8H), 1.79-1.89 (m, 8H), 4.06-4.11 (m, 8H), 6.71 (s, 1H), 6.92 (d, J = 8.4 Hz, 2H), 7.53-7.58 (m, 4H),
MALDI-TOF MS: m/z 513 ([M + H]+)
Anal. Calcd for C31H44O6: C, 72.62; H, 8.65. Found: C, 72.45; H, 8.48.
1 H NMR (CDCl 3 ) δ (ppm): 0.99 (t, J = 7.3 Hz, 12H), 1.46-1.59 (m, 8H), 1.79-1.89 (m, 8H), 4.06-4.11 (m, 8H) , 6.71 (s, 1H), 6.92 (d, J = 8.4 Hz, 2H), 7.53-7.58 (m, 4H),
MALDI-TOF MS: m / z 513 ([M + H] + )
Anal. Calcd for C 31 H 44 O 6 : C, 72.62; H, 8.65. Found: C, 72.45; H, 8.48.
(2)含窒素配位子[L−1]〜[L−5]の合成
合成例5
含窒素配位子[L−1]の合成
(2) Synthesis of nitrogen-containing ligands [L-1] to [L-5]
Synthesis example 5
Synthesis of nitrogen-containing ligand [L-1]
2-ヨードピリジン(1.58 g, 7.69 mmol)および Pd(PPh3)4(172 mg, 0.149 mmol)を200 mLの二口ナスフラスコに入れ、1,2-ジメトキシエタン(20 mL)を加えた。そこにジベンゾフラン-4-ボロン酸のエタノール溶液(0.354 M, 20 mL)および炭酸ナトリウム水溶液(2.00 M, 25 mL)を加え、窒素雰囲気下で6時間加熱還流させた。放冷した後、酢酸エチル(3×100 mL)で抽出を行い、有機層を水(2×100 mL)および飽和食塩水(100 mL) で順次洗浄した。この有機層を無水硫酸マグネシウムで乾燥させた後、ロータリーエバポレーターで溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって含窒素配位子[L−1]を淡黄色固体として得た (1.35 g, 5.50 mmol, 78%)。 2-Iodopyridine (1.58 g, 7.69 mmol) and Pd (PPh 3 ) 4 (172 mg, 0.149 mmol) were placed in a 200 mL two-necked eggplant flask, and 1,2-dimethoxyethane (20 mL) was added. Thereto were added an ethanol solution of dibenzofuran-4-boronic acid (0.354 M, 20 mL) and an aqueous sodium carbonate solution (2.00 M, 25 mL), and the mixture was heated to reflux for 6 hours under a nitrogen atmosphere. After allowing to cool, extraction was performed with ethyl acetate (3 × 100 mL), and the organic layer was washed successively with water (2 × 100 mL) and saturated brine (100 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off with a rotary evaporator. The obtained residue was purified by silica gel column chromatography (developing solvent; chloroform) to obtain nitrogen-containing ligand [L-1] as a pale yellow solid (1.35 g, 5.50 mmol, 78%).
1H NMR (CDCl3) δ (ppm): 7.29-7.32 (m, 1H), 7.38 (t, J = 7.7 Hz, 1H), 7.47-7.52 (m, 2H), 7.65 (d, J = 8.3 Hz, 1H), 7.88 (dt, J = 1.9 Hz and 7.8 Hz, 1H), 7.99-8.03 (m, 2H), 8.28 (dd, J = 1.1 Hz and 7.7 Hz, 1H) 8.42 (d, J = 8.3 Hz, 1H), 8.80 (m, 1H).
MALDI-TOF MS: m/z 246 ([M + H]+).
Anal. Calcd for C17H11NO: C, 83.25; H, 4.52; N, 5.71. Found: C, 83.33; H, 4.17; N, 5.46.
1 H NMR (CDCl 3 ) δ (ppm): 7.29-7.32 (m, 1H), 7.38 (t, J = 7.7 Hz, 1H), 7.47-7.52 (m, 2H), 7.65 (d, J = 8.3 Hz , 1H), 7.88 (dt, J = 1.9 Hz and 7.8 Hz, 1H), 7.99-8.03 (m, 2H), 8.28 (dd, J = 1.1 Hz and 7.7 Hz, 1H) 8.42 (d, J = 8.3 Hz , 1H), 8.80 (m, 1H).
MALDI-TOF MS: m / z 246 ([M + H] + ).
Anal. Calcd for C 17 H 11 NO: C, 83.25; H, 4.52; N, 5.71. Found: C, 83.33; H, 4.17; N, 5.46.
合成例6
含窒素配位子[L−2]の合成
Synthesis Example 6
Synthesis of nitrogen-containing ligand [L-2]
2-ヨードピリジン(410 mg, 2.00 mmol)および Pd(PPh3)4(38.7 mg, 0.0335 mmol)を100 mL の二口ナスフラスコに入れ、1,2-ジメトキシエタン(7 mL)を加えた。そこにチアンスレン-1-ボロン酸のエタノール溶液(0.286 M, 7 mL)および炭酸ナトリウム水溶液(2.00 M, 10 mL)を加え、窒素雰囲気下で18時間加熱還流させた。放冷後、酢酸エチル(3×100 mL)で抽出し、有機層を水(2×100 mL)および飽和食塩水(100 mL)で順次洗浄した。有機層を無水硫酸マグネシウムで乾燥させた後、溶媒をロータリーエバポレーターで留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム:ヘキサン=1:1, v/v)で精製することによって含窒素配位子[L−2]を白色固体として得た (302 g, 1.04 mmol, 52 %)。 2-Iodopyridine (410 mg, 2.00 mmol) and Pd (PPh 3 ) 4 (38.7 mg, 0.0335 mmol) were placed in a 100 mL two-necked eggplant flask, and 1,2-dimethoxyethane (7 mL) was added. An ethanol solution of thianslene-1-boronic acid (0.286 M, 7 mL) and an aqueous sodium carbonate solution (2.00 M, 10 mL) were added thereto, and the mixture was heated to reflux for 18 hours under a nitrogen atmosphere. After allowing to cool, the mixture was extracted with ethyl acetate (3 × 100 mL), and the organic layer was washed successively with water (2 × 100 mL) and saturated brine (100 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent is distilled off with a rotary evaporator, and the residue is purified by silica gel column chromatography (developing solvent; chloroform: hexane = 1: 1, v / v) to contain nitrogen. The ligand [L-2] was obtained as a white solid (302 g, 1.04 mmol, 52%).
1H NMR (CDCl3) δ (ppm): 7.15 (dt, J = 1.5 Hz and 7.4 Hz, 1H), 7.21 (dt, J = 1.5 Hz and 7.4 Hz, 1H), 7.28-7.36 (m, 3H), 7.45 (dd, J = 1.5 Hz and 4.4 Hz, 1H), 7.48 (dd, J = 1.5 Hz and 4.4 Hz, 1H), 7.53-7.58 (m, 2H), 7.81 (dt, J = 1.9 Hz and 7.7 Hz, 1H) 8.78 (ddd, J = 1.1 Hz, 1.9 Hz and 4.9 Hz, 1H)
MALDI-TOF MS: m/z 293 (M+)
Anal. Calcd for C17H11NS2: C, 69.59; H, 3.78; N, 4.77. Found: C, 69.58; H, 4.02; N, 4.77.
1 H NMR (CDCl 3 ) δ (ppm): 7.15 (dt, J = 1.5 Hz and 7.4 Hz, 1H), 7.21 (dt, J = 1.5 Hz and 7.4 Hz, 1H), 7.28-7.36 (m, 3H) , 7.45 (dd, J = 1.5 Hz and 4.4 Hz, 1H), 7.48 (dd, J = 1.5 Hz and 4.4 Hz, 1H), 7.53-7.58 (m, 2H), 7.81 (dt, J = 1.9 Hz and 7.7 Hz, 1H) 8.78 (ddd, J = 1.1 Hz, 1.9 Hz and 4.9 Hz, 1H)
MALDI-TOF MS: m / z 293 (M + )
Anal. Calcd for C 17 H 11 NS 2 : C, 69.59; H, 3.78; N, 4.77. Found: C, 69.58; H, 4.02; N, 4.77.
合成例7
含窒素配位子[L−3]の合成
Synthesis example 7
Synthesis of nitrogen-containing ligand [L-3]
2-ヨードピリジン(410 mg, 2.00 mmol)および Pd(PPh3)4(37.6 mg, 0.0325 mmol)を100 mL の二口ナスフラスコに入れ、1,2-ジメトキシエタン(7 mL)を加えた。そこにベンゾ[b]チオフェン-2-ボロン酸のエタノール溶液(0.303 M, 7 mL)および炭酸ナトリウム水溶液(2.00 M, 16 mL)を加え、窒素雰囲気下で22時間加熱還流させた。室温まで放冷した後、反応混合物を酢酸エチル(3×100 mL)で抽出し、有機層を水(2×100 mL)および飽和食塩水(100 mL)で順次洗浄した。有機層を無水硫酸マグネシウムで乾燥させた後、濾過にて固体を取り除いた。溶媒をロータリーエバポレーターで留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム:ヘキサン=1:1, v/v)で精製することによって含窒素配位子[L−3]を白色固体として得た(208 mg, 0.986 mmol, 50%)。 2-Iodopyridine (410 mg, 2.00 mmol) and Pd (PPh 3 ) 4 (37.6 mg, 0.0325 mmol) were placed in a 100 mL two-necked eggplant flask, and 1,2-dimethoxyethane (7 mL) was added. Thereto were added an ethanol solution of benzo [b] thiophene-2-boronic acid (0.303 M, 7 mL) and an aqueous sodium carbonate solution (2.00 M, 16 mL), and the mixture was heated to reflux for 22 hours under a nitrogen atmosphere. After allowing to cool to room temperature, the reaction mixture was extracted with ethyl acetate (3 × 100 mL), and the organic layer was washed successively with water (2 × 100 mL) and saturated brine (100 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solid was removed by filtration. The solvent was distilled off with a rotary evaporator, and the residue was purified by silica gel column chromatography (developing solvent; chloroform: hexane = 1: 1, v / v) to give the nitrogen-containing ligand [L-3] as a white solid. Obtained (208 mg, 0.986 mmol, 50%).
1H NMR (CDCl3) δ (ppm): 7.20-7.23 (m, 1H), 7.33-7.39 (m, 2H), 7.74 (dt, J = 1.7 Hz and 7.3 Hz, 1H), 7.80-7.82 (m, 2H), 7.84 (s, 1H), 7.86-7.89 (m, 1H), 8.64 (ddd, J = 1.0 Hz, 1.7 Hz and 4.8 Hz, 1H)
MALDI-TOF MS: m/z 212 ([M + H]+)
Anal. Calcd for C13H9NS: C, 73.90; H, 4.29; N, 6.63. Found: C, 73.83; H, 4.61; N, 6.38.
1 H NMR (CDCl 3 ) δ (ppm): 7.20-7.23 (m, 1H), 7.33-7.39 (m, 2H), 7.74 (dt, J = 1.7 Hz and 7.3 Hz, 1H), 7.80-7.82 (m , 2H), 7.84 (s, 1H), 7.86-7.89 (m, 1H), 8.64 (ddd, J = 1.0 Hz, 1.7 Hz and 4.8 Hz, 1H)
MALDI-TOF MS: m / z 212 ([M + H] + )
Anal. Calcd for C 13 H 9 NS: C, 73.90; H, 4.29; N, 6.63. Found: C, 73.83; H, 4.61; N, 6.38.
合成例8
含窒素配位子[L−4]の合成
Synthesis example 8
Synthesis of nitrogen-containing ligand [L-4]
1−クロロイソキノリン(1.11 g, 6.72 mmol)および Pd(PPh3)4(198 mg, 0.172 mmol)を100 mL の二口ナスフラスコに入れ、1,2-ジメトキシエタン(15 mL)を加えた。そこへチオフェン-2-ボロン酸のエタノール溶液(0.335 M,15 mL)および炭酸ナトリウム水溶液(2.00 M, 15 mL)を加え、窒素雰囲気下で22時間加熱還流させた。室温まで放冷した後、反応混合物を酢酸エチル(3×100 mL)で抽出し、有機層を水(2×200 mL)および飽和食塩水(200 mL)で順次洗浄した。有機層を無水硫酸マグネシウムで乾燥させた後、濾過にて固体を取り除いた。溶媒をロータリーエバポレーターで留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって含窒素配位子[L−4]を白色固体として得た(913 mg, 4.32 mmol, 86%)。 1-chloroisoquinoline (1.11 g, 6.72 mmol) and Pd (PPh 3 ) 4 (198 mg, 0.172 mmol) were placed in a 100 mL two-necked eggplant flask, and 1,2-dimethoxyethane (15 mL) was added. Thereto were added an ethanol solution of thiophene-2-boronic acid (0.335 M, 15 mL) and an aqueous sodium carbonate solution (2.00 M, 15 mL), and the mixture was heated to reflux for 22 hours under a nitrogen atmosphere. After allowing to cool to room temperature, the reaction mixture was extracted with ethyl acetate (3 × 100 mL), and the organic layer was washed successively with water (2 × 200 mL) and saturated brine (200 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solid was removed by filtration. The solvent was distilled off using a rotary evaporator, and the residue was purified by silica gel column chromatography (developing solvent; chloroform) to obtain nitrogen-containing ligand [L-4] as a white solid (913 mg, 4.32 mmol, 86 %).
1H NMR (CDCl3) δ (ppm): 7.20-7.23 (dd, J = 3.7 Hz and 5.1 Hz, 1H), 7.54 (d, J = 5.1 Hz, 1H), 7.58-7.64 (m, 3H), 7.70 (t, J = 7.7 Hz, 1H), 7.87 (d, J = 8.1 Hz,1H), 8.52 (d, J = 8.1 Hz, 1H), 8.55 (d, J = 5.1 Hz, 1H)
MALDI-TOF MS: m/z 211 (M+)
Anal. Calcd for C13H9NS: C, 73.90; H, 4.29; N, 6.63. Found: C, 74.21; H, 3.99; N, 6.24.
1 H NMR (CDCl 3 ) δ (ppm): 7.20-7.23 (dd, J = 3.7 Hz and 5.1 Hz, 1H), 7.54 (d, J = 5.1 Hz, 1H), 7.58-7.64 (m, 3H), 7.70 (t, J = 7.7 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 8.52 (d, J = 8.1 Hz, 1H), 8.55 (d, J = 5.1 Hz, 1H)
MALDI-TOF MS: m / z 211 (M + )
Anal. Calcd for C 13 H 9 NS: C, 73.90; H, 4.29; N, 6.63. Found: C, 74.21; H, 3.99; N, 6.24.
合成例9
含窒素配位子[L−5]の合成
Synthesis Example 9
Synthesis of nitrogen-containing ligand [L-5]
1−クロロイソキノリン(341 mg, 2.08 mmol)および Pd(PPh3)4(73.5 mg, 0.064 mmol)を100 mL の二口ナスフラスコに入れ、1,2-ジメトキシエタン(7 mL)を加えた。そこにベンゾ[b]チオフェン-2-ボロン酸のエタノール溶液(0.289 M,7 mL)および炭酸ナトリウム水溶液(2.00 M, 7 mL)を加え、窒素雰囲気下で15時間加熱還流させた。室温まで放冷した後、反応混合物を酢酸エチル(3×100 mL)で抽出し、有機層を水(2×100 mL)および飽和食塩水(100 mL)で順次洗浄した。有機層を無水硫酸マグネシウムで乾燥させた後、濾過にて固体を取り除いた。溶媒をロータリーエバポレーターで留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって含窒素配位子[L−5]を白色固体として得た(297 mg, 1.13 mmol, 56%)。 1-chloroisoquinoline (341 mg, 2.08 mmol) and Pd (PPh 3 ) 4 (73.5 mg, 0.064 mmol) were placed in a 100 mL two-necked eggplant flask, and 1,2-dimethoxyethane (7 mL) was added. To this were added an ethanol solution of benzo [b] thiophene-2-boronic acid (0.289 M, 7 mL) and an aqueous sodium carbonate solution (2.00 M, 7 mL), and the mixture was heated to reflux for 15 hours under a nitrogen atmosphere. After allowing to cool to room temperature, the reaction mixture was extracted with ethyl acetate (3 × 100 mL), and the organic layer was washed successively with water (2 × 100 mL) and saturated brine (100 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solid was removed by filtration. The solvent was distilled off using a rotary evaporator, and the residue was purified by silica gel column chromatography (developing solvent; chloroform) to obtain nitrogen-containing ligand [L-5] as a white solid (297 mg, 1.13 mmol, 56 %).
1H NMR (CDCl3) δ (ppm): 7.38-7.45(m, 2H), 7.64-7.77 (m, 3H), 7.85 (s, 1H), 7.88-7.95 (m, 3H), 8.61-8.64 (m, 2H)
MALDI-TOF MS: m/z 261 (M+)
Anal. Calcd for C17H11NS: C, 78.13; H, 4.24; N, 5.36. Found: C, 78.35; H, 4.11; N, 5.45.
1 H NMR (CDCl 3 ) δ (ppm): 7.38-7.45 (m, 2H), 7.64-7.77 (m, 3H), 7.85 (s, 1H), 7.88-7.95 (m, 3H), 8.61-8.64 ( m, 2H)
MALDI-TOF MS: m / z 261 (M + )
Anal. Calcd for C 17 H 11 NS: C, 78.13; H, 4.24; N, 5.36. Found: C, 78.35; H, 4.11; N, 5.45.
(3)[前駆体−1]〜[前駆体−5]の合成
製造例1
[前駆体−1]の合成
(3) Synthesis of [Precursor-1] to [Precursor-5]
Production Example 1
Synthesis of [Precursor-1]
含窒素配位子[L−1](1.49 g, 6.07 mmol)を300 mLの二口ナスフラスコに入れ、2-エトキシエタノール(120 mL)を加え、攪拌した。そこへK2PtCl4 の水溶液(59.3 mM, 40 mL)を加え、混合物を窒素雰囲気下で11時間150℃で加熱還流させた。放冷後、水(300 mL)を加えると緑色固体が析出した。析出した固体を濾過によって集め、メタノール(50 mL)およびヘキサン(50 mL)で順次洗浄し、[前駆体−1]を淡緑色固体として得た(1.193 g, 1.66 mmol, 70 %)。 Nitrogen-containing ligand [L-1] (1.49 g, 6.07 mmol) was put into a 300 mL two-necked eggplant flask, and 2-ethoxyethanol (120 mL) was added and stirred. Thereto was added an aqueous solution of K 2 PtCl 4 (59.3 mM, 40 mL), and the mixture was heated to reflux at 150 ° C. for 11 hours under a nitrogen atmosphere. After allowing to cool, water (300 mL) was added to precipitate a green solid. The precipitated solid was collected by filtration and washed successively with methanol (50 mL) and hexane (50 mL) to give [Precursor-1] as a pale green solid (1.193 g, 1.66 mmol, 70%).
1H NMR (CDCl3) δ (ppm): 6.32 (d, J = 8.1 Hz, 1H), 7.13 (m, 1H), 7.19-7.30 (m, 3H), 7.32-7.37 (m, 2H), 7.42-7.52 (m, 3H), 7.58 (d, J = 8.3 Hz, 1H), 7.66 (m, 1H), 7.81-7.89 (m, 3H) 8.05-8.10 (m, 2H), 8.49 (d, J = 8.3 Hz, 1H), 8.81 (dd, J = 1.1 Hz and 8.1 Hz, 1H), 9.40 (d, J = 5.1 Hz, 1H), 9.72 (d, J = 5.1 Hz, 1H).
MALDI-TOF MS: m/z 720 ([M + H]+)
Anal. Calcd for C34H21O2N2PtCl: C, 56.71; H, 2.94; N, 3.89. Found: C, 56.43; H, 3.12; N, 3.72
1 H NMR (CDCl 3 ) δ (ppm): 6.32 (d, J = 8.1 Hz, 1H), 7.13 (m, 1H), 7.19-7.30 (m, 3H), 7.32-7.37 (m, 2H), 7.42 -7.52 (m, 3H), 7.58 (d, J = 8.3 Hz, 1H), 7.66 (m, 1H), 7.81-7.89 (m, 3H) 8.05-8.10 (m, 2H), 8.49 (d, J = 8.3 Hz, 1H), 8.81 (dd, J = 1.1 Hz and 8.1 Hz, 1H), 9.40 (d, J = 5.1 Hz, 1H), 9.72 (d, J = 5.1 Hz, 1H).
MALDI-TOF MS: m / z 720 ([M + H] + )
Anal. Calcd for C 34 H 21 O 2 N 2 PtCl: C, 56.71; H, 2.94; N, 3.89. Found: C, 56.43; H, 3.12; N, 3.72
製造例2
[前駆体−2]の合成
Production Example 2
Synthesis of [Precursor-2]
含窒素配位子[L−2](747 mg, 2.55 mmol)を100 ml の二口ナスフラスコに入れ、2-エトキシエタノール(45 mL)を加え、攪拌した。そこにK2PtCl4 の水溶液(76.0 mM, 15 mL)を加え、窒素雰囲気下で21時間150℃で加熱還流させた。放冷後、水(200 mL)を加えると橙色固体が析出した。析出した固体をろ過によって集め、メタノール(100 mL)およびヘキサン(100 ml)で順次洗浄し、[前駆体-2]を橙色固体として得た(831 mg, 1.02 mmol, 90 %)。
MALDI-TOF MS: m/z 780 ([M Cl]+)
Anal. Calcd for C34H21N2S4PtCl: C, 50.02; H, 2.59; N, 3.43. Found: C, 50.12; H, 2.78; N, 3.28.
Nitrogen-containing ligand [L-2] (747 mg, 2.55 mmol) was placed in a 100 ml two-necked eggplant flask, and 2-ethoxyethanol (45 mL) was added and stirred. Thereto was added an aqueous solution of K 2 PtCl 4 (76.0 mM, 15 mL), and the mixture was heated to reflux at 150 ° C. for 21 hours under a nitrogen atmosphere. After allowing to cool, water (200 mL) was added to precipitate an orange solid. The precipitated solid was collected by filtration and washed successively with methanol (100 mL) and hexane (100 ml) to give [Precursor-2] as an orange solid (831 mg, 1.02 mmol, 90%).
MALDI-TOF MS: m / z 780 ([M Cl] + )
Anal. Calcd for C 34 H 21 N 2 S 4 PtCl: C, 50.02; H, 2.59; N, 3.43. Found: C, 50.12; H, 2.78; N, 3.28.
製造例3
[前駆体−3]の合成
Production Example 3
Synthesis of [Precursor-3]
含窒素配位子[L−3](790 mg, 3.74 mmol)を200 mLの二口ナスフラスコに入れ、2-エトキシエタノール(75 mL)を加え、攪拌した。そこに、K2PtCl4 の水溶液(38.5 mM, 25 mL)を加え、窒素雰囲気下で13時間150℃で加熱還流させた。放冷後、水(300 mL)を加えると緑色固体が析出した。析出した固体をろ過によって集め、メタノール(200 mL)およびヘキサン(200 mL)で順次洗浄し、淡緑色固体として得た(461 mg, 0.709 mmol, 74 %)。 Nitrogen-containing ligand [L-3] (790 mg, 3.74 mmol) was placed in a 200 mL two-necked eggplant flask, and 2-ethoxyethanol (75 mL) was added and stirred. Thereto was added an aqueous solution of K 2 PtCl 4 (38.5 mM, 25 mL), and the mixture was heated to reflux at 150 ° C. for 13 hours under a nitrogen atmosphere. After allowing to cool, water (300 mL) was added to precipitate a green solid. The precipitated solid was collected by filtration and washed successively with methanol (200 mL) and hexane (200 mL) to give a pale green solid (461 mg, 0.709 mmol, 74%).
1H NMR (CDCl3) δ (ppm): 6.13 (d, J = 8.0 Hz, 1H), 6.90 (t, J =7.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.28-7.30 (m, 2H), 7.33-7.37 (m, 2H), 7.70-7.79 (m, 4H), 7.99-8.05 (m, 2H), 8.17 (s, 1H), 9.40 (d, J = 5.6 Hz, 1H) 9.59 (d, J = 5.6 Hz, 1H)
TOF MS: m/z 615 ([M Cl]+)
Anal. Calcd for C26H17N2S2PtCl: C, 47.89; H, 2.63; N, 4.30. Found: C, 47.72; H, 2.63; N, 4.22.
1 H NMR (CDCl 3 ) δ (ppm): 6.13 (d, J = 8.0 Hz, 1H), 6.90 (t, J = 7.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.18 ( t, J = 7.5 Hz, 1H), 7.28-7.30 (m, 2H), 7.33-7.37 (m, 2H), 7.70-7.79 (m, 4H), 7.99-8.05 (m, 2H), 8.17 (s, 1H), 9.40 (d, J = 5.6 Hz, 1H) 9.59 (d, J = 5.6 Hz, 1H)
TOF MS: m / z 615 ([M Cl] + )
Anal. Calcd for C 26 H 17 N 2 S 2 PtCl: C, 47.89; H, 2.63; N, 4.30. Found: C, 47.72; H, 2.63; N, 4.22.
製造例4
[前駆体−4]の合成
Production Example 4
Synthesis of [Precursor-4]
含窒素配位子[L−4](616 mg, 2.92 mmol)を100 mLの二口ナスフラスコに入れ、2-エトキシエタノール(30 mL)を加え、攪拌した。そこに、K2PtCl4 の水溶液(147 mM, 10 mL)を加え、窒素雰囲気下で12時間150℃で加熱還流させた。放冷後、水(200 mL)を加えると黄褐色固体が析出した。析出した固体をろ過によって集め、メタノール(200 mL)およびヘキサン(200mL)で順次洗浄し、黄褐色固体として得た(898 mg, 1.37 mmol, 94 %)。 Nitrogen-containing ligand [L-4] (616 mg, 2.92 mmol) was placed in a 100 mL two-necked eggplant flask, and 2-ethoxyethanol (30 mL) was added and stirred. Thereto was added an aqueous solution of K 2 PtCl 4 (147 mM, 10 mL), and the mixture was heated to reflux at 150 ° C. for 12 hours under a nitrogen atmosphere. After allowing to cool, water (200 mL) was added to precipitate a tan solid. The precipitated solid was collected by filtration and washed successively with methanol (200 mL) and hexane (200 mL) to give a tan solid (898 mg, 1.37 mmol, 94%).
1H NMR (CDCl3) δ (ppm): 6.14 (d, J = 4.9 Hz, 1H), 7.07 (dd, J = 3.7 Hz and 4.9 Hz, 1H), 7.30-7.33 (m, J = 6.6 Hz, 1H), 7.38 (t, J = 5.1 Hz, 1H), 7.48 (dd, J = 0.9 Hz and 5.1 Hz,1H), 7.59-7.80 (m, 6H), 7.86 (m, 1H), 7.97 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 8.61 (d, J = 8.3 Hz,1H), 9.04 (d, J = 6.6 Hz, 1H) 9.45 (d, J = 6.6 Hz, 1H)
TOF MS: m/z 616 ([M Cl]+)
Anal. Calcd for C26H17N2S2PtCl: C, 47.89; H, 2.63; N, 4.30. Found: C, 47.75; H, 2.82; N, 4.15.
1 H NMR (CDCl 3 ) δ (ppm): 6.14 (d, J = 4.9 Hz, 1H), 7.07 (dd, J = 3.7 Hz and 4.9 Hz, 1H), 7.30-7.33 (m, J = 6.6 Hz, 1H), 7.38 (t, J = 5.1 Hz, 1H), 7.48 (dd, J = 0.9 Hz and 5.1 Hz, 1H), 7.59-7.80 (m, 6H), 7.86 (m, 1H), 7.97 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 9.04 (d, J = 6.6 Hz, 1H) 9.45 (d, J = 6.6 Hz, 1H)
TOF MS: m / z 616 ([M Cl] + )
Anal.Calcd for C 26 H 17 N 2 S 2 PtCl: C, 47.89; H, 2.63; N, 4.30. Found: C, 47.75; H, 2.82; N, 4.15.
製造例5
[前駆体−5]の合成
Production Example 5
Synthesis of [Precursor-5]
含窒素配位子[L−5](503 mg, 1.92 mmol)を100 mLの二口ナスフラスコに入れ、2-エトキシエタノール(20 mL)を加え、攪拌した。そこに、K2PtCl4 の水溶液(147 mM, 7 mL)を加え、窒素雰囲気下で9時間150℃で加熱還流させた。放冷後、水(300 mL)を加えると赤色固体が析出した。析出した固体をろ過によって集め、メタノール(100 mL)およびヘキサン(100 mL)で順次洗浄し、赤色固体として得た(588 mg, 0.782 mmol, 76 %)。 Nitrogen-containing ligand [L-5] (503 mg, 1.92 mmol) was placed in a 100 mL two-necked eggplant flask, and 2-ethoxyethanol (20 mL) was added and stirred. Thereto was added an aqueous solution of K 2 PtCl 4 (147 mM, 7 mL), and the mixture was heated to reflux at 150 ° C. for 9 hours under a nitrogen atmosphere. After allowing to cool, water (300 mL) was added to precipitate a red solid. The precipitated solid was collected by filtration and washed successively with methanol (100 mL) and hexane (100 mL) to give a red solid (588 mg, 0.782 mmol, 76%).
1H NMR (CDCl3) δ (ppm): 6.14 (d, J = 8.0 Hz, 1H), 6.79 (t, J = 7.7 Hz, 1H), 7.21 (t, J = 7.7 Hz, 1H), 7.27-7.30 (m, 2H), 7.60-7.94 (m, 11H), 8.03-8.07 (m, 2H), 8.75 (d, J = 8.5 Hz, 1H), 9.21 (d, J = 6.6 Hz, 1H), 9.55 (d, J = 6.6 Hz, 1H)
TOF MS: m/z 716 ([M Cl]+)
Anal. Calcd for C34H21N2S2PtCl: C, 54.29; H, 2.81; N, 3.72. Found: C, 54.30; H, 2.78; N, 3.53.
1 H NMR (CDCl 3 ) δ (ppm): 6.14 (d, J = 8.0 Hz, 1H), 6.79 (t, J = 7.7 Hz, 1H), 7.21 (t, J = 7.7 Hz, 1H), 7.27- 7.30 (m, 2H), 7.60-7.94 (m, 11H), 8.03-8.07 (m, 2H), 8.75 (d, J = 8.5 Hz, 1H), 9.21 (d, J = 6.6 Hz, 1H), 9.55 (d, J = 6.6 Hz, 1H)
TOF MS: m / z 716 ([M Cl] + )
Anal.Calcd for C 34 H 21 N 2 S 2 PtCl: C, 54.29; H, 2.81; N, 3.72. Found: C, 54.30; H, 2.78; N, 3.53.
(4)白金(II)錯体[1−1]〜[1−5]の合成
実施例1
白金錯体化合物[1-1]の合成
(4) Synthesis of platinum (II) complexes [1-1] to [1-5]
Example 1
Synthesis of platinum complex compound [1-1]
前駆体-1(300 mg, 0.417 mmol)、1,3-ビス(3,4-ジブトキシフェニル)プロパン-1,3-ジオン(426 mg, 0.832 mmol)、および酸化銀(I)(147 mg, 0.63 mmol)の混合物を窒素雰囲気下、2-エトキシエタノール(30 mL)中、110 ℃にて20時間攪拌した。放冷後、水(200 mL)およびクロロホルム(200 mL)を加え、混合物を分液ロート中で激しく振盪した。有機層を分離し、水層をさらにクロロホルムで抽出した(3 × 100 mL)。全ての有機層を混合し、水(2 × 100 mL)および飽和食塩水(100 mL)で洗浄後、無水硫酸マグネシウムで乾燥させた。固体を濾過にて除去した後、ロータリーエバポレーターで溶媒を留去した。残渣をシリカゲルクロマトグラフィー(展開溶媒;クロロホルム)で精製することによって白金錯体[1−1]を黄色の固体として得た(収量;172 mg)。
収率: 43%.
Precursor-1 (300 mg, 0.417 mmol), 1,3-bis (3,4-dibutoxyphenyl) propane-1,3-dione (426 mg, 0.832 mmol), and silver (I) oxide (147 mg , 0.63 mmol) was stirred in 2-ethoxyethanol (30 mL) at 110 ° C. for 20 hours under a nitrogen atmosphere. After allowing to cool, water (200 mL) and chloroform (200 mL) were added, and the mixture was vigorously shaken in a separatory funnel. The organic layer was separated and the aqueous layer was further extracted with chloroform (3 × 100 mL). All organic layers were mixed, washed with water (2 × 100 mL) and saturated brine (100 mL), and dried over anhydrous magnesium sulfate. The solid was removed by filtration, and then the solvent was distilled off with a rotary evaporator. The residue was purified by silica gel chromatography (developing solvent; chloroform) to obtain platinum complex [1-1] as a yellow solid (yield; 172 mg).
Yield: 43%.
1H NMR (CDCl3) δ(ppm): 0.99-1.07 (m, 12H), 1.49-1.64 (m, 8H), 1.83-1.95 (m, 8H), 4.08-4.21 (m, 8H), 6.67 (s, 1H), 6.93-6.96 (m, 2H), 7.17 (t, J = 5.9 Hz, 1H), 7.34 (t, J = 7.1 Hz, 1H), 7.43 (t, J = 7.1 Hz, 1H), 7.59-7.67 (m, 4H), 7.75-7.83 (m, 3H), 7.92-7.98 (m, 2H),8.61 (d, J = 8.0 Hz, 1H),9.22 (d, J = 5.9 Hz, 1H).
MALDI-TOF MS: m/z 950 (M+).
発光極大波長 λmax: 518 nm(励起波長 λex = 369 nm).
1 H NMR (CDCl 3 ) δ (ppm): 0.99-1.07 (m, 12H), 1.49-1.64 (m, 8H), 1.83-1.95 (m, 8H), 4.08-4.21 (m, 8H), 6.67 ( s, 1H), 6.93-6.96 (m, 2H), 7.17 (t, J = 5.9 Hz, 1H), 7.34 (t, J = 7.1 Hz, 1H), 7.43 (t, J = 7.1 Hz, 1H), 7.59-7.67 (m, 4H), 7.75-7.83 (m, 3H), 7.92-7.98 (m, 2H), 8.61 (d, J = 8.0 Hz, 1H), 9.22 (d, J = 5.9 Hz, 1H) .
MALDI-TOF MS: m / z 950 (M + ).
Maximum emission wavelength λ max : 518 nm (excitation wavelength λ ex = 369 nm).
実施例2
白金錯体化合物[1−2]の合成
Example 2
Synthesis of platinum complex compound [1-2]
上記反応式に従って、白金錯体化合物[1−1]の合成と同様の方法で白金錯体化合物[1−2]を黄色の固体として得た。
収率: 51%.
According to the above reaction formula, platinum complex compound [1-2] was obtained as a yellow solid by the same method as the synthesis of platinum complex compound [1-1].
Yield: 51%.
1H NMR (CDCl3) δ(ppm): 0.98-1.05 (m, 12H), 1.47-1.63 (m, 8H), 1.81-1.93 (m, 8H), 4.07-4.16 (m, 8H), 6.63 (s, 1H), 6.93 (t, J = 7.3 Hz, 2H), 7.16-7.39 (m, 3H), 7.56-7.66 (m, 7H), 7.82 (d, J = 7.9 Hz, 1H), 7.97 ( t, J = 8.2 Hz, 1H), 9.24 (d, J = 8.8 Hz, 1H), 9.34 (d, J = 6.2 Hz, 1H),
MALDI-TOF MS: m/z 999 ([M + H]+).
発光極大波長 λmax: 518 nm(励起波長 λex = 365 nm).
1 H NMR (CDCl 3 ) δ (ppm): 0.98-1.05 (m, 12H), 1.47-1.63 (m, 8H), 1.81-1.93 (m, 8H), 4.07-4.16 (m, 8H), 6.63 ( s, 1H), 6.93 (t, J = 7.3 Hz, 2H), 7.16-7.39 (m, 3H), 7.56-7.66 (m, 7H), 7.82 (d, J = 7.9 Hz, 1H), 7.97 (t , J = 8.2 Hz, 1H), 9.24 (d, J = 8.8 Hz, 1H), 9.34 (d, J = 6.2 Hz, 1H),
MALDI-TOF MS: m / z 999 ([M + H] + ).
Maximum emission wavelength λ max : 518 nm (excitation wavelength λ ex = 365 nm).
実施例3
白金錯体化合物[1−3]の合成
Example 3
Synthesis of platinum complex compound [1-3]
上記反応式に従って、白金錯体化合物[1-1]の合成と同様の方法で白金錯体化合物[1−3]を黄色の固体として得た。
収率: 37%.
According to the above reaction formula, platinum complex compound [1-3] was obtained as a yellow solid by the same method as the synthesis of platinum complex compound [1-1].
Yield: 37%.
1H NMR (CDCl3) δ(ppm): 0.96-1.04 (m, 12H), 1.47-1.60 (m, 8H), 1.82-1.91 (m, 8H), 4.07-4.13 (m, 8H), 6.63 (s, 1H), 6.92-6.96 (m, 3H), 7.24-7.28 (m, 1H), 7.31-7.35 (m, 2H), 7.54 (dd, J = 1.8 Hz and 8.3 Hz, 1H), 7.59 (d, J = 1.8 Hz, 1H), 7.62 (dd, J = 1.8 Hz and 8.3 Hz, 1H), 7.67 (d, J = 1.8 Hz, 1H),7.71 (dt, J = 1.2 Hz and 7.8 Hz , 1H), 7.82 (d, J = 7.8 Hz, 1H), 8.95 (d, J = 7.8 Hz,1H), 9.09 (d, J = 5.6 Hz,1H)
MALDI-TOF MS: m/z 917 ([M + H]+).
発光極大波長 λmax: 615 nm(励起波長 λex = 378 nm).
1 H NMR (CDCl 3 ) δ (ppm): 0.96-1.04 (m, 12H), 1.47-1.60 (m, 8H), 1.82-1.91 (m, 8H), 4.07-4.13 (m, 8H), 6.63 ( s, 1H), 6.92-6.96 (m, 3H), 7.24-7.28 (m, 1H), 7.31-7.35 (m, 2H), 7.54 (dd, J = 1.8 Hz and 8.3 Hz, 1H), 7.59 (d , J = 1.8 Hz, 1H), 7.62 (dd, J = 1.8 Hz and 8.3 Hz, 1H), 7.67 (d, J = 1.8 Hz, 1H), 7.71 (dt, J = 1.2 Hz and 7.8 Hz, 1H) , 7.82 (d, J = 7.8 Hz, 1H), 8.95 (d, J = 7.8 Hz, 1H), 9.09 (d, J = 5.6 Hz, 1H)
MALDI-TOF MS: m / z 917 ([M + H] + ).
Maximum emission wavelength λ max : 615 nm (excitation wavelength λ ex = 378 nm).
実施例4
白金錯体化合物[1−4]の合成
Example 4
Synthesis of platinum complex compound [1-4]
上記反応式に従って、白金錯体化合物[1−1]の合成と同様の方法で白金錯体化合物[1−4]を橙色の固体として得た。
収率: 42%.
According to the above reaction formula, platinum complex compound [1-4] was obtained as an orange solid by the same method as the synthesis of platinum complex compound [1-1].
Yield: 42%.
1H NMR (CDCl3) δ(ppm): 0.98-1.05 (m, 12H), 1.51-1.61 (m, 8H), 1.82-1.93 (m, 8H), 4.07-4.18 (m, 8H), 6.71 (s, 1H), 6.91-6.97 (m, 2H), 7.33 (d, J = 6.5 Hz, 1H), 7.46 (d, J = 5.1 Hz, 1H), 7.64-7.82 (m, 8H), 8.68 (d, J = 8.3 Hz, 1H), 8.96 (d, J = 7.3 Hz, 1H).
MALDI-TOF MS: m/z 917 ([M + H]+).
発光極大波長 λmax: 658 nm(励起波長 λex = 402 nm).
1 H NMR (CDCl 3 ) δ (ppm): 0.98-1.05 (m, 12H), 1.51-1.61 (m, 8H), 1.82-1.93 (m, 8H), 4.07-4.18 (m, 8H), 6.71 ( s, 1H), 6.91-6.97 (m, 2H), 7.33 (d, J = 6.5 Hz, 1H), 7.46 (d, J = 5.1 Hz, 1H), 7.64-7.82 (m, 8H), 8.68 (d , J = 8.3 Hz, 1H), 8.96 (d, J = 7.3 Hz, 1H).
MALDI-TOF MS: m / z 917 ([M + H] + ).
Maximum emission wavelength λ max : 658 nm (excitation wavelength λ ex = 402 nm).
実施例5
白金錯体化合物[1−5]の合成
Example 5
Synthesis of platinum complex compound [1-5]
上記反応式に従って、白金錯体化合物[1−1]の合成と同様の方法で白金錯体化合物[1−5]を橙色の固体として得た。
収率: 91%.
According to the above reaction formula, platinum complex compound [1-5] was obtained as an orange solid by the same method as the synthesis of platinum complex compound [1-1].
Yield: 91%.
1H NMR (CDCl3) δ(ppm): 0.96-1.05 (m, 12H), 1.49-1.62 (m, 8H), 1.82-1.93 (m, 8H), 4.09-4.17 (m, 8H), 6.66 (s, 1H), 6.93-6.96 (m, 2H), 7.26-7.31 (m, 2H), 7.38 (t, J = 7.6 Hz, 8H), 7.57 (dd, J = 1.7 Hz and 8.3 Hz, 1H), 7.65-7.74 (m, 5H), 7.79 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 8.80 (d, J = 8.0 Hz, 1H), 9.11 (d, J = 6.6 Hz, 1H), 9.15 (d, J = 8.3 Hz, 1H),
MALDI-TOF MS: m/z 966 (M+).
発光極大波長 λmax: 709 nm(励起波長 λex = 509 nm).
1 H NMR (CDCl 3 ) δ (ppm): 0.96-1.05 (m, 12H), 1.49-1.62 (m, 8H), 1.82-1.93 (m, 8H), 4.09-4.17 (m, 8H), 6.66 ( s, 1H), 6.93-6.96 (m, 2H), 7.26-7.31 (m, 2H), 7.38 (t, J = 7.6 Hz, 8H), 7.57 (dd, J = 1.7 Hz and 8.3 Hz, 1H), 7.65-7.74 (m, 5H), 7.79 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 8.80 (d, J = 8.0 Hz, 1H), 9.11 (d, J = 6.6 Hz, 1H), 9.15 (d, J = 8.3 Hz, 1H),
MALDI-TOF MS: m / z 966 (M + ).
Maximum emission wavelength λ max : 709 nm (excitation wavelength λ ex = 509 nm).
実施例6
白金錯体化合物[1−1]による有機EL素子の作製
図1に示す構造を有する有機電界発光素子を以下の方法で作製した。ガラス基板上にインジウム・スズ酸化物(ITO)透明導電膜を60nm堆積したもの(三容真空社製;シート抵抗60Ω、20×25×1(ガラス膜厚)mm)を通常のフォトリソグラフィ技術と亜鉛-塩酸エッチングを用いて8mm幅のストライプにパターニングして陽極を形成した。パターン形成したITO基板を、純水による水洗、メタノールによる超音波洗浄、イソプロピルアルコールによるソックスレー洗浄の順で洗浄後、窒素ブローで乾燥させた。最後に硫酸、過酸化水素/アンモニア水による表面親水化を行った後、スピンコーター内に設置した。
Example 6
Production of Organic EL Device Using Platinum Complex Compound [1-1] An organic electroluminescent device having the structure shown in FIG. 1 was produced by the following method. A 60 nm thick indium tin oxide (ITO) transparent conductive film deposited on a glass substrate (manufactured by Sanyo Vacuum Co., Ltd .; sheet resistance 60Ω, 20 × 25 × 1 (glass film thickness) mm) An anode was formed by patterning into stripes with a width of 8 mm using zinc-hydrochloric acid etching. The patterned ITO substrate was washed in the order of water washing with pure water, ultrasonic washing with methanol, and Soxhlet washing with isopropyl alcohol, and then dried by nitrogen blowing. Finally, the surface was hydrophilized with sulfuric acid, hydrogen peroxide / ammonia water, and then placed in a spin coater.
その上に、ポリ(エチレンジオキシチオフェン):ポリ(スチレン・スルフォン酸)(PEDOT:PSS)(ティーエーケミカル株式会社製、Baytron P HC V4)をスピンコートした(厚さ30nm)。スピンコートの条件は次のとおりであった。温度25℃、回転速度3000回転/分、回転時間60秒。
以下に、PEDOT:PSSの構造式を示す。
On top of that, poly (ethylenedioxythiophene): poly (styrene sulfonic acid) (PEDOT: PSS) (manufactured by TA Chemical Co., Ltd., Baytron P HC V4) was spin-coated (thickness 30 nm). The conditions for spin coating were as follows. Temperature 25 ° C, rotation speed 3000 rotations / minute, rotation time 60 seconds.
The structural formula of PEDOT: PSS is shown below.
次に、白金錯体Pt1(0.1wt%)と2-(4-ビフェニリル)-5-(4-tert-ブチルフェニル)-1,3,4,-オキサジアゾール(PBD、29.9wt%、東京化成株式会社)をポリビニルカルバゾ-ル(PVCz、Mw35000、70wt%、シグマーアルドリッチ株式会社)に分散させたトルエン溶液をスピンコートして色素薄膜を作製した(120nm)。以下に、PVCz、PBD、Pt1の構造式を示す。 Next, platinum complex Pt1 (0.1 wt%) and 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4, -oxadiazole (PBD, 29.9 wt%, Tokyo Kasei) A dye thin film was prepared by spin-coating a toluene solution in which polyvinyl carbazole (PVCz, Mw35000, 70 wt%, Sigma Aldrich Co., Ltd.) was dispersed. The structural formulas of PVCz, PBD, and Pt1 are shown below.
ここで、スピンコートを行った素子を、陰極蒸着用のマスクとして2mm幅のストライプ状シャドーマスクを、陽極のITOストライプと直交するように素子に密着させて、真空蒸着装置内に設置して装置内の真空度が1×10-6Torr以下になるまで排気した。続いて、銀をモリブデンボートボートを用いて膜厚100nmとなるようにして蒸着し、陰極を作製した。蒸着時の真空度は4×10-6 Torrであった。陰極蒸着時の基板温度は室温に保持した。以上の様にして、8mm×2mmのサイズの発光面積部分を有する有機電界発光素子が得られた。得られた有機電界発光素子の概略を図1に示す。
図1において、有機電界発光素子は、基板11、陽極12、ポリ(エチレンジオキシチオフェン):ポリ(スチレン・スルフォン酸)(PEDOT:PSS)の層13、白金錯体Pt1(0.1wt%)と2-(4-ビフェニリル)-5-(4-tert-ブチルフェニル)-1,3,4,-オキサジアゾール(PBD、29.9wt%、東京化成株式会社)をポリビニルカルバゾ-ル(PVCz、Mw35000、70wt%、シグマーアルドリッチ株式会社)に分散させた層14、陰極15を有する。層13はホール注入輸送層として働き、層14は発光層として働く。
この有機電界発光素子の輝度を測定した。有機電界発光素子の最大輝度は13.7 cd/m2であった。
Here, the device on which the spin coating was applied was used as a mask for cathode vapor deposition, and a 2 mm wide stripe-shaped shadow mask was brought into close contact with the device so as to be orthogonal to the ITO ITO stripe and installed in a vacuum vapor deposition apparatus. The inside was evacuated until the degree of vacuum became 1 × 10 −6 Torr or less. Subsequently, silver was deposited using a molybdenum boat so as to have a film thickness of 100 nm, thereby producing a cathode. The degree of vacuum at the time of vapor deposition was 4 × 10 −6 Torr. The substrate temperature during cathode deposition was kept at room temperature. As described above, an organic electroluminescent element having a light emitting area portion having a size of 8 mm × 2 mm was obtained. The outline of the obtained organic electroluminescent element is shown in FIG.
In FIG. 1, an organic electroluminescent device includes a
The luminance of this organic electroluminescent element was measured. The maximum luminance of the organic electroluminescent device was 13.7 cd / m 2 .
11 基板、 12 陽極、 13 PEDOT:PSSの層、
14 発光層、 15 陰極
11 substrate, 12 anode, 13 PEDOT: PSS layer,
14 light emitting layer, 15 cathode
Claims (15)
[式中、
Mは、二価または三価の金属原子、
A1は、芳香環または複素環であり、
A2は、複素環であり、
R1およびR2は、同一または異なって、アルキル基またはアリール基であり、R1およびR2の少なくとも一方は、アリール基であり、
mおよびnは1または2であり、mとnの合計は金属原子の価数(2または3)である。]
で示される金属錯体化合物。 General formula:
[Where:
M is a divalent or trivalent metal atom,
A 1 is an aromatic ring or a heterocyclic ring,
A 2 is a heterocycle,
R 1 and R 2 are the same or different and are an alkyl group or an aryl group, and at least one of R 1 and R 2 is an aryl group,
m and n are 1 or 2, and the sum of m and n is the valence (2 or 3) of the metal atom. ]
A metal complex compound represented by
[式中、
A1は、芳香環または複素環であり、
A2は、複素環であり、
R1およびR2は、同一または異なって、アルキル基またはアリール基であり、R1およびR2の少なくとも一方は、アリール基である。]
で示される金属錯体化合物。 Formula (II):
[Where:
A 1 is an aromatic ring or a heterocyclic ring,
A 2 is a heterocycle,
R 1 and R 2 are the same or different and are an alkyl group or an aryl group, and at least one of R 1 and R 2 is an aryl group. ]
A metal complex compound represented by
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