WO2023179479A1 - 金属铂配合物、有机光电器件及显示或照明装置 - Google Patents
金属铂配合物、有机光电器件及显示或照明装置 Download PDFInfo
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- WO2023179479A1 WO2023179479A1 PCT/CN2023/082146 CN2023082146W WO2023179479A1 WO 2023179479 A1 WO2023179479 A1 WO 2023179479A1 CN 2023082146 W CN2023082146 W CN 2023082146W WO 2023179479 A1 WO2023179479 A1 WO 2023179479A1
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- Prior art keywords
- platinum complex
- group
- substituted
- heteroaryl
- metal platinum
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 41
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- -1 nitro, cyano , amino Chemical group 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 36
- 125000001072 heteroaryl group Chemical group 0.000 claims description 33
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000000304 alkynyl group Chemical group 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- 230000005693 optoelectronics Effects 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 150000002527 isonitriles Chemical class 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000004986 diarylamino group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 239000003446 ligand Substances 0.000 abstract description 14
- WJWVMGIAUYAQLA-UHFFFAOYSA-N 8-phenylquinoline Chemical group C1=CC=CC=C1C1=CC=CC2=CC=CN=C12 WJWVMGIAUYAQLA-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 102
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 77
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 53
- 150000001875 compounds Chemical class 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- 239000010410 layer Substances 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- 125000001424 substituent group Chemical group 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000012043 crude product Substances 0.000 description 20
- 239000003480 eluent Substances 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- 238000010898 silica gel chromatography Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 238000003775 Density Functional Theory Methods 0.000 description 10
- 238000004770 highest occupied molecular orbital Methods 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 8
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 8
- 125000000464 thioxo group Chemical group S=* 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 230000005281 excited state Effects 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 238000005284 basis set Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N isonitrile group Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HJBGZJMKTOMQRR-UHFFFAOYSA-N (3-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=O)=C1 HJBGZJMKTOMQRR-UHFFFAOYSA-N 0.000 description 1
- 125000004502 1,2,3-oxadiazolyl group Chemical group 0.000 description 1
- 125000004511 1,2,3-thiadiazolyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=NC=C1)* 0.000 description 1
- 125000004506 1,2,5-oxadiazolyl group Chemical group 0.000 description 1
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- 125000001781 1,3,4-oxadiazolyl group Chemical group 0.000 description 1
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- CSAJUFLXZFOWKO-UHFFFAOYSA-N 3-methyl-4h-imidazol-5-one Chemical compound CN1CC(=O)N=C1 CSAJUFLXZFOWKO-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
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- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004090 cyclononenyl group Chemical group C1(=CCCCCCCC1)* 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Definitions
- the present invention relates to a metal platinum complex, and in particular to a metal platinum complex, an organic photoelectric device and a display or lighting device.
- OLED Organic Light-Emitting Diode
- LCD Organic Light-Emitting Diode
- OLED has achieved rapid development in recent years. Compared with LCD display technology, OLED has the following advantages: autonomous light-emitting, no backlight required, energy-saving; foldable or bendable; fast response speed , high contrast; wide operating temperature range; low material cost, high luminous efficiency, etc.
- OLED has become a new generation of full-color display and lighting technology and has received widespread attention from academia and industry. It has been widely used in flat panel displays, solid lighting, military and aerospace fields, and is expected to replace LCDs in the future ( Liquid Crystal Display, LCD).
- fluorescent materials In the early stages of OLED development, traditional fluorescent materials were mainly used, which have good device stability. However, fluorescent materials can theoretically only utilize up to 25% of singlet excitons, and the remaining 75% of triplet excitons can only be deactivated through non-radiative transitions due to transition prohibition, which limits their application in OLEDs. Due to the spin-orbit coupling effect (SOC) of heavy metals, cyclometallic platinum complex phosphorescent materials can break the triplet transition barrier, effectively promote the intersystem jump of electrons from the singlet state to the triplet state, and make full use of electrical excitation. All singlet and triplet excitons are generated, allowing the maximum theoretical quantum efficiency to reach 100%.
- SOC spin-orbit coupling effect
- the ligands of cyclometal platinum complex phosphorescent materials include luminescent groups and auxiliary groups, and changes in their chemical structure will affect the electronic structure of the complex, thereby affecting its photophysical properties.
- the four-tooth ring metal structure can effectively reduce vibration coupling, suppress non-radiative attenuation, help increase the radiation rate, and achieve high quantum efficiency phosphorescence emission.
- the four-tooth ring metal platinum complex phosphorescent materials have made great progress, so far, stable and efficient platinum complex phosphorescent materials are still extremely limited. Therefore, the development of new four-tooth ring metal structure platinum complex has great impact on the OLED industry. Development remains vital.
- the purpose of the present invention is to provide a tetradentate ring metal platinum complex phosphorescent material and an organic light-emitting device based on an 8-phenylquinoline derivative.
- the tetradentate ring metal platinum complex phosphorescent material provided by the present invention includes a compound represented by the following general formula (1),
- Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 and Y 16 are each independently for CH or N;
- R 1 , R 2 , R 3 , R 4 and R 5 each independently represent mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted, and R 1 , R 2 , R 3 , R 4 and R 5 is each independently hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, Amino, mono or dialkylamino, mono or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkyl Oxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl,
- X represents NR a , O, S; among them, R a represents hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, and hydroxyl , mercapto group, alkoxy group, aryloxy group, haloalkyl group, ester group, nitrile group, isonitrile group, heteroaryl group, alkoxycarbonyl group, amido group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonyl group Amino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, polymeric groups, or other combination; and can be independently or selectively connected to
- Z represents O, S, NR b ; wherein, R b represents hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl , mercapto group, alkoxy group, aryloxy group, haloalkyl group, ester group, nitrile group, isonitrile group, heteroaryl group, alkoxycarbonyl group, amido group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonyl group Amino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, polymeric groups, or other combination; and can be independently or selectively connected to adjacent R
- the phosphorescent material is any one of the following structural formulas:
- the invention provides an organic optoelectronic device, which includes:
- the organic functional layer contains the organometallic complex of the present invention.
- the invention provides an organic optoelectronic device, which includes a cathode layer, an anode layer and an organic layer.
- the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer or an active layer, an electron injection layer, and an electron transport layer. At least one layer, wherein any layer of the device contains the organometallic complex of the present invention.
- the organic optoelectronic device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor or an organic memory device, preferably an organic light-emitting diode device or a luminescent electrochemical cell.
- the light-emitting layer contains the organic metal complex and the corresponding host material, wherein the mass percentage of the organic metal complex is between 1% and 50%.
- the present invention also provides an organic light-emitting device, which has a light-emitting layer containing the metal platinum complex of the present invention on a substrate.
- the invention also provides a device comprising the metal platinum complex of the invention.
- the device is a full-color display, a photovoltaic device, a light-emitting display device or an organic light-emitting diode.
- it includes at least one cathode, at least one anode and at least one luminescent layer, at least one of said luminescent layers comprising the metal platinum complex of the invention.
- the device is an organic light-emitting diode, the light-emitting layer of which contains the metal platinum complex and the corresponding host material, wherein the mass percentage of the metal platinum complex is between 1% and 50%, and there is no limit on the host material.
- the invention also provides the application of organic metal complexes in the production of organic optoelectronic devices.
- the present invention further provides a display or lighting device containing the organic optoelectronic device of the present invention.
- a phosphorescent material based on a tetradentate ring metal platinum complex based on an 8-phenylquinoline derivative is used in an organic light-emitting device.
- the organic light-emitting device is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.
- the present invention develops a new 6/5/7 metal paracyclic structure using 8-phenylquinoline structure and its derivatives, benzo five-membered heterocyclic ring and phenolic oxygen tetradentate ligand, and obtains A new class of four-tooth ring metal platinum complex phosphorescent materials.
- Figure 1 is an emission spectrum diagram of the metal platinum (II) phosphorescent luminescent material in Example 1 of the present invention in a dichloromethane solution in a deoxygenated state at room temperature;
- Figure 2a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-1 respectively;
- Figure 3a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-77 respectively;
- Figure 4a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-49 respectively;
- Figure 5a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-61 respectively;
- Figure 6a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-79 respectively;
- Figure 7a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-80 respectively;
- Figure 8a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-101 respectively;
- Figure 9a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-113 respectively;
- Figure 10a-b are schematic diagrams of the HOMO and LUMO orbital distributions of compound Pt-114 respectively;
- Figure 11 is a schematic structural diagram of the organic light-emitting device of the present invention.
- the terms "optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which the stated event or circumstance occurs and instances in which it does not occur.
- compositions described in this invention are disclosed, as well as the compositions themselves to be used in the methods disclosed in this invention.
- These and other materials are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these materials are disclosed, although specific reference to each different individual and aggregate combination and arrangement of these compounds cannot be specifically disclosed. , but each has its own special assumptions and descriptions. For example, if a specific compound is disclosed and discussed, and the many modifications that can be made to many molecules containing that compound are discussed, then every combination and permutation of that compound and possible modifications are specifically considered, unless specifically stated to the contrary. possible modifications.
- the linking atoms used in the present invention are capable of linking two groups, for example, N and C.
- the linking atom can optionally (if valency permitting) attach other chemical groups.
- an oxygen atom would not have any other chemical groups attached because the valence bond is already satisfied once two atoms (eg, N or C) are bonded.
- carbon is the linking atom
- two additional chemical groups can be attached to the carbon atom.
- cyclic structure refers to any cyclic chemical structure, including but not limited to aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene and N-heterocyclyl. Ring carbine.
- permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds.
- exemplary substituents include those described below.
- the permissible substituents may be one or more, the same or different.
- a heteroatom eg, nitrogen
- the present invention is not intended to be limited in any way by the permissible substituents of organic compounds.
- substituted or “substituted with” includes the implicit proviso that such substitution is consistent with the permissible valence bonds of the substituting atom and the substituent, and that the substitution results in a stable compound (e.g., one that does not spontaneously undergo transformation) For example, compounds by rearrangement, cyclization, elimination, etc.).
- individual substituents can be further optionally substituted (ie, further substituted or unsubstituted) unless expressly stated to the contrary.
- R 1 ”, “R 2 ”, “R 3 ” and “R 4 ” are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in the present invention, and when they are defined as certain substituents in one example, they can also be defined as some other substituents in another example.
- alkyl used in the present invention refers to a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl Alkyl, eicosyl, tetradecyl, etc.
- the alkyl group may be cyclic or acyclic.
- the alkyl group may be branched or unbranched.
- the alkyl group may also be substituted or unsubstituted.
- the alkyl group may substitute one or more groups, including but not Limited to optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo groups and mercapto groups described in the present invention.
- a "lower alkyl” group is an alkyl group containing 1 to 6 (eg, 1 to 4) carbon atoms.
- alkyl generally refers to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituents on the alkyl group.
- halogenated alkyl or “haloalkyl” specifically refers to an alkyl group substituted with one or more halogens (eg, fluorine, chlorine, bromine, or iodine).
- alkoxyalkyl specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below.
- alkylamino specifically refers to an alkyl group substituted with one or more amino groups, as described below, etc.
- alkyl is used in one context and a specific term such as “alkyl alcohol” is used in another context, it is not meant to imply that the term “alkyl” does not also refer to a specific term such as “alkyl” Alcohol” etc.
- cycloalkyl as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms consisting of at least three carbon atoms.
- examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like.
- heterocycloalkyl is a class of cycloalkyl groups as defined above and is included within the meaning of the term “cycloalkyl” in which at least one ring carbon atom is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus replace.
- the cycloalkyl and heterocycloalkyl groups may be substituted or unsubstituted.
- the cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro as described in the present invention. , silyl group, thio-oxo group and mercapto group.
- polyolefin group refers to a group containing two or more CH 2 groups attached to each other.
- Polyolefin group may be expressed as -(CH 2 ) a -, where "a” is an integer between 2 and 500.
- alkoxy and alkoxy group refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through ether bonds; that is, “alkoxy” may be defined as— OR 1 , where R 1 is alkyl or cycloalkyl as defined above.
- Alkoxy also includes the alkoxy polymers just described; i.e., the alkoxy group may be a polyether, such as -OR 1 -OR 2 or -OR 1 -(OR 2 ) a -OR 3 , where "a" is an integer from 1 to 500, and R 1 , R 2 and R 3 are each independently an alkyl group, a cycloalkyl group or a combination thereof.
- alkenyl as used herein is a hydrocarbon group of 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon double bond.
- the alkenyl group may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or thiol.
- groups including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or thiol.
- Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like.
- heterocycloalkenyl is a class of cycloalkenyl groups as defined above and is included within the meaning of the term “cycloalkenyl” in which at least one carbon atom of the ring is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus substitution. Cycloalkenyl and heterocycloalkenyl groups may be substituted or unsubstituted.
- This cylindrite and heterothenelvide can replace one or more groups, including but not limited to the alkyl, cyclotomyl, alkyl, alumoxyl, cyclopenne, cycloprobal, ring, cyclone, cyclopyrum, cyclone, cyclone, cyclone, cyclone, cyclopae, cyclopa, Alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or mercapto group.
- groups including but not limited to the alkyl, cyclotomyl, alkyl, alumoxyl, cyclopenne, cycloprobal, ring, cyclone, cyclopyrum, cyclone, cyclone, cyclone, cyclone, cyclopae, cyclo
- alkynyl as used herein is a hydrocarbon group having 2 to 30 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
- the alkynyl group may be unsubstituted or substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, and alkynyl as described in the present invention. , cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or mercapto group.
- cycloalkynyl as used herein is a non-aromatic carbon-based ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond.
- examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononenyl, and the like.
- heterocycloalkynyl is a cycloalkenyl group as defined above and is included within the meaning of the term “cycloalkynyl” in which at least one of the carbon atoms of the ring is replaced by a heteroatom, said heteroatom Atoms such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus.
- Cycloalkynyl and heterocycloalkynyl groups may be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, and alkyne described in the present invention. radical, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or mercapto group.
- aryl used in the present invention refers to any carbon-based aromatic group with 60 carbon atoms or less, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, etc.
- aryl also includes “heteroaryl” which is defined as an aromatic group containing at least one heteroatom within the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- non-heteroaryl (which is also included in the term “aryl”) defines an aromatic-containing group that does not contain heteroatoms.
- Aryl groups may be substituted or unsubstituted.
- the aryl group may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, Aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo group or mercapto group.
- bias is a specific type of aryl group and is included in the definition of "aryl”. Biaryl refers to two aryl groups joined together by a fused ring structure, as in naphthalene, or by one or more carbon-carbon bonds, as in biphenyl.
- amine or “amino” used in the present invention is represented by the formula -NR 1 R 2 , wherein R 1 and R 2 can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, Choose from cycloalkynyl, aryl or heteroaryl.
- alkylamino as used herein is represented by the formula -NH(-alkyl), where the alkyl group is as described herein.
- Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, isopentyl Amino, tert-pentylamino, hexylamino, etc.
- dialkylamino as used in the present invention is represented by the formula -N(-alkyl) 2 , wherein the alkyl group is as described in the present invention.
- Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino , Dipentylamino, Diisopentylamino, Di-tert-pentylamino, Dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N -Propylamino etc.
- carboxylic acid as used herein is represented by the formula -C(O)OH.
- esters used in the present invention is represented by the formula -OC(O)R 1 or -C(O)OR 1 , wherein R 1 can be an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group as described in the present invention. , alkynyl, cycloalkynyl, aryl or heteroaryl.
- polyester as used herein is represented by the formula - (R 1 O(O)CR 2 -C(O)O) a - or - (R 1 O(O)CR 2 -OC(O)) a - , wherein R 1 and R 2 can be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl according to the present invention and "a” is 1 to An integer of 500.
- the term “polyester” is used to describe groups produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.
- ether used in the present invention is represented by the formula R 1 OR 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described in the present invention. base, aryl or heteroaryl.
- polyether used in the present invention is represented by the formula - (R 1 OR 2 O) a -, wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl as described in the present invention. radical, alkynyl, cycloalkynyl, aryl or heteroaryl and "a" is an integer from 1 to 500.
- polyether groups include polyoxyethylene, polyoxypropylene and polyoxybutylene.
- halogen refers to the halogens fluorine, chlorine, bromine and iodine.
- heterocyclyl refers to monocyclic and polycyclic non-aromatic ring systems
- heteroaryl refers to monocyclic and polycyclic non-aromatic ring systems of not more than 60 carbon atoms.
- An aromatic ring system in which at least one of the ring members is not carbon.
- the term includes azetidinyl, Dioxanyl, furyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and 1,3,4-oxadiazolyl (oxazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, Tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl Tetrazolyl, including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl, thi
- hydroxyl as used herein is represented by the formula -OH.
- ketone used in the present invention is represented by the formula R 1 C(O) R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, or alkyne as described in the present invention. base, cycloalkynyl, aryl or heteroaryl.
- azido used in the present invention is represented by the formula -N3 .
- nitro as used herein is represented by the formula -NO2 .
- nitrile as used herein is represented by the formula -CN.
- sil used in the present invention is represented by the formula - SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 can independently be hydrogen or an alkyl, cycloalkyl, alkoxy group as described in the present invention. radical, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
- thio-oxo group as used herein is represented by the formula —S(O)R 1 , —S(O) 2 R 1 , —OS(O) 2 R 1 or —OS(O) 2 OR 1 , wherein R 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention.
- R 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention.
- sulfonyl used in the present invention refers to a sulfur-oxo group represented by the formula -S(O) 2 R 1 , where R 1 can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne base, cycloalkynyl, aryl or heteroaryl.
- sulfone used in the present invention is represented by the formula R 1 S(O) 2 R 2 , where R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.
- sulfoxide used in the present invention is represented by the formula R 1 S(O)R 2 , wherein R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.
- mercapto group used in the present invention is represented by the formula -SH.
- R 1 ”, “R 2 ”, “R 3 ”, and “R n ” (where n is an integer) used in the present invention may independently have one or more of the groups listed above.
- R 1 is a straight chain alkyl group
- one hydrogen atom of the alkyl group may be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halogen, or the like.
- the first group may be incorporated within the second group, or the first group may be pendant (ie, attached) to the second group.
- the amino group may be bonded within the backbone of the alkyl group.
- the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded in or linked to the second group.
- the compounds described herein may contain "optionally substituted” moieties.
- substituted (whether preceded by the term “optionally” or not) means that one or more hydrogens of the specified moiety are substituted with a suitable substituent.
- an "optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be selected from one of the specified groups When the above substituents are substituted, the substituents may be the same or different at each position.
- Combinations of substituents contemplated by this invention are preferably combinations that form stable or chemically feasible compounds. It is also contemplated that, in certain aspects, each substituent may be further optionally substituted (ie, further substituted or unsubstituted) unless expressly stated to the contrary.
- n is usually an integer. That is, Rn is understood to mean five individual substituents Rn (a) , Rn (b) , Rn (c) , Rn (d) , Rn (e) . "Individual substituent" means that each R substituent can be independently defined. For example, if R n(a) is halogen in one instance, then R n(b) need not be halogen in that instance.
- R1 , R2 , R3 , R4 , R5 , R6 , etc. are mentioned several times in the chemical structures and units disclosed and described herein. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. in the specification applies to any structure referencing R 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. respectively or unit unless otherwise stated.
- organic optoelectronic devices using organic materials are becoming increasingly urgent for several reasons. Many of the materials used to make such devices are relatively cheap, so organic optoelectronic devices have the potential to be cost-effective compared to inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, can make them well suited for special applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic light-emitting layer emits light can generally be easily tuned using appropriate dopants.
- blue electroluminescent devices remain the most challenging area of the technology to date, and the stability of blue devices is a major issue. It has been proven that the choice of host material is very important for the stability of blue devices. However, the lowest energy of the triplet excited state (T 1 ) of the blue luminescent material is very high, which means that the lowest energy of the triplet excited state (T 1 ) of the host material of the blue device should be higher. This makes it more difficult to develop main materials for blue devices.
- the metal complexes of the present invention can be customized or tuned to specific applications where specific emission or absorption properties are desired.
- the optical properties of the metal complexes of the present disclosure can be tuned by changing the structure of the ligand surrounding the metal center or by changing the structure of the fluorescent emitter on the ligand.
- metal complexes with ligands with electron-donating substituents or electron-withdrawing substituents can often exhibit different optical properties in emission and absorption spectra.
- the color of metal complexes can be adjusted by modifying the conjugated groups on the fluorescent emitters and ligands.
- the emission of such complexes of the invention can be modulated, for example from ultraviolet to near infrared, by changing the ligand or phosphor structure.
- a phosphor is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, where singlet excitons rapidly decay to produce instantaneous light emission.
- the complexes of the present invention provide emission across a large portion of the visible spectrum.
- the complexes of the present invention can emit light in the range of about 400 nm to about 700 nm.
- the complexes of the present invention have improved stability and efficiency relative to traditional emissive complexes.
- the complexes of the invention can be used as luminescent labels for example in biological applications, anticancer agents, emitters in organic light-emitting diodes (OLEDs) or combinations thereof.
- the complexes of the present invention can be used in light-emitting devices, such as compact fluorescent lamps (CFLs), light-emitting diodes (LEDs), incandescent lamps, and combinations thereof.
- Disclosed herein are compounds or composite complexes containing platinum.
- the terms compound or complex are used interchangeably herein. Additionally, the compounds disclosed herein have a neutral charge.
- the compounds disclosed herein can exhibit desired properties and have emission and/or absorption that can be modulated by selection of appropriate ligands. Spectrum. In another aspect, the invention may exclude any compound or compounds, structures or portions thereof specifically recited herein.
- the compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of compatible light absorption and emission, and Used as markers for biological applications.
- light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of compatible light absorption and emission, and Used as markers for biological applications.
- OLEDs organic light emitting diodes
- the disclosed compounds are platinum complexes.
- the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.
- the compounds disclosed herein are useful in a variety of applications.
- the compound can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.
- OLEDs organic light-emitting diodes
- the compounds of the present invention can be prepared using a variety of methods, including, but not limited to, those described in the examples provided herein.
- Compounds disclosed herein may be delayed fluorescent and/or phosphorescent emitters.
- the compounds disclosed herein can be delayed fluorescent emitters.
- the compounds disclosed herein can be phosphorescent emitters.
- the compounds disclosed herein can be delayed fluorescent emitters and phosphorescent emitters.
- the present disclosure relates to cyclometallic platinum complexes, which can be used as luminescent materials and host materials in OLED devices.
- the method for preparing the disclosed compounds described in this example is one of many methods. There are many other methods for preparing the disclosed compounds, and this application does not delimit the scope. Accordingly, one skilled in the art to which this disclosure belongs can readily modify the methods described or utilize different methods to prepare one or more of the disclosed compounds. The following methods are exemplary only. Temperatures, catalysts, concentrations, reactant compositions, and other process conditions can be changed, and for the desired compounds, those skilled in the art to which this disclosure belongs can easily select appropriate reactants and conditions. preparation.
- Pt-17 can emit strong orange-red light; its polymethyl methacrylate (PMMA) film has a quantum efficiency greater than 80% and can be reused as an OLED light-emitting layer material.
- PMMA polymethyl methacrylate
- DFT density functional theory
- Each layer of the organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion plating and other methods, or wet film forming methods such as spin coating, printing, printing and other methods.
- the solvent used is not particularly limited.
- the OLED device of the present invention contains a hole transport layer.
- the hole transport material can be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but does not represent the present invention. Limited to the following structures:
- the hole transport layer contained in the OLED device of the present invention contains one or more p-type dopants.
- the preferred p-type dopant of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:
- the electron transport layer can be selected from at least one compound ET-1 to ET-13, but this does not mean that the present invention is limited to the following structure:
- the electron transport layer can be formed of organic materials and one or more n-type dopants (such as LiQ).
- OLED device examples are:
- the structure of the specific implementation of the bottom-emitting OLED device is on glass containing ITO.
- the hole injection layer (HIL) is HT-1:P-3 (95:5v/v%) with a thickness of 10 nanometers;
- the hole transport layer ( HTL) is HT-1 with a thickness of 90 nanometers;
- the electron blocking layer (EBL) is HT-10 with a thickness of 10 nanometers, and
- the luminescent layer (EML) is the main material (RH): the platinum metal complex of the present invention (95:5v /v%), the thickness is 35 nm, the electron transport layer (ETL) is ET-13:LiQ (50:50v/v%), the thickness is 35 nm, and then the cathode Al is evaporated to 70 nm.
- the main body material (RH) can be selected from the following structures:
- the produced organic light-emitting device was tested for voltage, efficiency and life under the current condition of 10mA/ cm2 using standard methods known in the art.
- the device structures in the above embodiments and comparative examples are consistent except for the different light-emitting layers.
- the performance of the device based on PtON11Me is used as a reference.
- the device containing the divalent platinum metal complex of the present invention has better performance than The current efficiency of conventional organic light-emitting devices has been significantly improved, and its lifespan has also been improved.
- the novel divalent platinum metal complex in the present invention has great application value in organic optoelectronic devices.
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Abstract
提供了一种金属铂配合物、有机发光器件及显示或照明装置,采用8-苯基喹啉结构及衍生物和苯并五元杂环及酚氧四齿配体发展了6/5/7金属并环结构,得到一类四齿环金属铂配合物磷光材料。所述磷光材料的化学式结构如通式(1)所示。
Description
本发明涉及一种金属铂配合物,尤其涉及一种金属铂配合物、有机光电器件及显示或照明装置。
有机发光二极管(Organic Light-Emitting Diode,OLED)近些年取得了突飞猛进地发展,相比于LCD显示技术,OLED具有如下优势:自主发光,无需背光源,节能;可折叠或弯曲;响应速度快,对比度高;工作温度范围宽;材料成本低、发光效率高等。OLED已成为新一代的全彩显示和照明技术,受到学术界和工业界的广泛重视,其在平板显示、固体照明、军事和航空航天领域得到了广泛的应用,并且有望在未来取代液晶显示器(Liquid Crystal Display,LCD)。
在OLED发展初期,主要采用传统荧光材料,该材料具有很好的器件稳定性。但是荧光材料理论上最多只能利用25%的单重态激子,剩余75%的三重态激子因跃迁禁阻只能通过非辐射跃迁失活,限制了其在OLED中的应用。而环金属铂配合物磷光材料由于其重金属的自旋轨道耦合效应(SOC),可以打破三线态跃迁禁阻,能有效促进电子由单线态到三线态的系间蹿越,充分利用电致激发产生的所有单线态和三线态激子,使其最大理论量子效率可达100%。通常,环金属铂配合物磷光材料的配体包括发光基团和辅助基团,其化学结构的变化会影响配合物的电子结构,进而影响其光物理性质。相比于二齿与三齿结构,四齿环金属结构可以有效减小振动耦合,抑制非辐射衰减,利于提高辐射速率,实现高量子效率的磷光发射。虽然目前四齿环金属铂配合物磷光材料已经取得了长足的发展,但是至今为止,稳定而高效的铂配合物磷光材料还极其有限,因此开发新型四齿环金属结构铂配合物对OLED产业的发展依然具有举足轻重的意义。
发明内容
为了开发更多种类、更高性能的磷光材料,本发明的目的在于提供一种基于8-苯基喹啉衍生物的四齿环金属铂配合物磷光材料及有机发光器件。
本发明提供的四齿环金属铂配合物磷光材料包含下述通式(1)所表示的化合物,
其中,
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15和Y16各自独立地为CH或
N;
R1、R2、R3、R4和R5各自独立地表示单基取代、双基取代、三基取代、四基取代或者无取代,且R1、R2、R3、R4和R5各自独立地为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且两个或者多个邻近的R1、R2、R3、R4和R5各自独立或者选择性连接形成稠环。
X表示NRa、O、S;其中,Ra表示为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且可与邻近的R3和R4各自独立或者选择性连接形成稠环。
Z表示O、S、NRb;其中,Rb表示为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且可与邻近的R1和R5各自独立或者选择性连接形成稠环。
优选地,所述磷光材料为下述结构式中的任意一种:
本发明提供了一种有机光电器件,其包括:
第一电极;
第二电极,其与所述第一电极相面对;
有机功能层,其夹设于所述第一电极和所述第二电极之间;
其中,所述有机功能层包含本发明的有机金属配合物。
本发明提供了一种有机光电器件,其包括阴极层、阳极层和有机层,所述有机层包括空穴注入层、空穴传输层、发光层或活性层、电子注入层、电子传输层中至少一层,其中,该器件的任一层中含有本发明的有机金属配合物。
优选地,所述有机光电器件为有机光伏器件、有机发光器件、有机太阳电池、电子纸、有机感光体、有机薄膜晶体管或有机内存器件,优选为有机发光二极管器件或发光电化学电池。
优选地,所述发光层中含有所述有机金属配合物和相应的主体材料,其中所述有机金属配合物的质量百分数在1%至50%。
本发明又提供了一种有机发光器件,在基板上具有包含本发明的金属铂配合物的发光层。
本发明又提供了一种器件,其包含本发明的金属铂配合物。
优选地,所述器件为全彩显示器、光伏器件、发光显示器件或有机发光二极管。
优选地,其包括至少一个阴极、至少一个阳极和至少一层发光层,所述发光层中的至少一层包括本发明的金属铂配合物。
优选地,所述器件为有机发光二极管,其发光层中含有所述的金属铂配合物和相应的主体材料,其中金属铂配合物的质量百分数在1%至50%,主体材料没有任何限制。本发明又提供了有机金属配合物在制作有机光电器件中的应用。
本发明进一步提供了显示或照明装置,其含有本发明的有机光电器件。
优选的,基于8-苯基喹啉衍生物的四齿环金属铂配合物磷光材料在有机发光器件中的应用。所述有机发光器件为有机发光二极管、发光二极管或发光电化学电池。
与现有技术相比,本发明采用8-苯基喹啉构及其衍生物和苯并五元杂环及酚氧四齿配体发展了新的6/5/7金属并环结构,得到一类新的四齿环金属铂配合物磷光材料。
图1为本发明实施例1中金属铂(II)磷光发光材料室温下在二氯甲烷溶液中除氧状态下的发射光谱图;
图2a-b分别为化合物Pt-1的HOMO、LUMO轨道分布示意图;
图3a-b分别为化合物Pt-77的HOMO、LUMO轨道分布示意图;
图4a-b分别为化合物Pt-49的HOMO、LUMO轨道分布示意图;
图5a-b分别为化合物Pt-61的HOMO、LUMO轨道分布示意图;
图6a-b分别为化合物Pt-79的HOMO、LUMO轨道分布示意图;
图7a-b分别为化合物Pt-80的HOMO、LUMO轨道分布示意图;
图8a-b分别为化合物Pt-101的HOMO、LUMO轨道分布示意图;
图9a-b分别为化合物Pt-113的HOMO、LUMO轨道分布示意图;
图10a-b分别为化合物Pt-114的HOMO、LUMO轨道分布示意图;
图11为本发明的有机发光器件的结构示意图。
通过参考以下具体实施方式和其中包含的实施例,可以更容易地理解本公开。在公开和描述本发明的化合物、器件和/或方法之前,应当明白,除非另有说明,否则他们不限于具体的合成方法或者具体的试剂,因为这是可以变化的。也应当明白本发明中使用的术语仅是用于描述特定方面,并不旨在限制。尽管本发明描述的那些类似或者等价的任何方法和材料都可用于该实践或者试验,但现在描述了示例方法和材料。
在说明书和所附权利要求中所用的术语单数形式“一种”、“一个”和“所述”包含复数指代,否则上下文中会另有明确指出。因此,例如提及“组分”时包含两种或多种组分的混合物。
本发明所使用的术语“任选的”或“任选地”意味着随后描述的事件或情况可以或不发生,并且该描述包括所述事件或情况发生的实例及它未发生的实例。
公开了可用于制备本发明所述的组合物的组分,以及要用于本发明中公开的方法中的组合物本身。本发明公开了这些和其它材料,并且应当理解公开了这些物质的组合、子集、相互作用、组等,虽然不能具体地公开这些化合物的每个不同的单独和总的组合以及排列的具体参考,但各自有专门的设想和描述。例如,如果公开和讨论了具体的化合物,并且讨论了能够对许多包含该化合物的分子进行的许多修饰,那么具体地考虑了该化合物的每种组合和排列以及可能进行的修饰,除非特别指出相反的可能修饰。因此,如果公开了一类分子A、B和C以及一类分子D、E和F,和组合分子A-D的实例,那么即使没有单独地记载每一个,但也考虑公开了每个单独地和总的含义组合,A-E、A-F、B-D、B-E、B-F、C-D、C-E和C-F。同样地,也公开了任何子集或这些的组合。例如,A-E、B-F和C-E的子组也是公开的。这一概念适用于本发明的所有方面,包括但不限于制备和使用该组合物的方法中的步骤。因此,如果存在各种另外的步骤能够进行,应当理解,这些另外的步骤各自能够以该方法的具体实施方式或者实施方式的组合进行。
本发明使用的连接原子能够连接两个基团,例如,连接N和C。该连接原子能够任选地(如果价键允许)附接其他的化学基团。例如,氧原子不会具有任何其它的化学基团附接,因为一旦键合两个原子(例如,N或C)价键则已经满足。相反,当碳是连接原子时,两个另外的化学基团能够附接至该碳原子。合适的化学基团包括但不限于氢、羟基、烷基、烷氧基、=O、卤素、硝基、胺、酰胺、巯基、芳基、杂芳基、环烷基和杂环基。
本发明使用的术语“环状结构”或类似术语是指任何环状化学结构,其包括但不限于芳基、杂芳基、环烷基、环烯基、杂环基、卡宾和N-杂环卡宾。
本发明使用的术语“取代的”或类似术语包含有机化合物的所有允许的取代基。广义上,允许的取代基包括有机化合物的环状和非环状、支链和非支链、碳环和杂环、芳香族和非芳香族取代基。例如,示例性取代基包括以下所述。对于合适的有机化合物来说,允许的取代基可为一个或多个,相同或不同。对于本发明的目的而言,杂原子(例如氮)能够具有氢取代基和/或本发明所述满足该杂原子价键的有机化合物的任何允许取代基。本发明不意图以任何方式用有机化合物允许的取代基来进行任何限制。同样,术语“取代”或“取代有”包含隐含条件是这种取代符合取代的原子和该取代基的允许的价键,和该取代导致稳定的化合物(例如,不会自发地进行转化(例如通过重排、环化、消去等)的化合物)。在某些方面,除非明确指出相反,否则,单独的取代基能够进一步任选地取代(即,进一步取代或未取代的)。
在定义各种术语时,“R1”、“R2”、“R3”和“R4”在本发明中作为通用符号来表示各种特定的取代基。这些符号能够是任何取代基,不限于本发明公开的那些,当它们在一个实例中被定义为某些取代基时,在另一个实例中也可以被定义为一些其他取代基。
本发明使用的术语“烷基”是1至30个碳原子的支链或非支链的饱和烃基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基、十六烷基、二十烷基、二十四烷基等。该烷基可为环状或非环状。该烷基可为支链或非支链的。该烷基也可为取代或未取代的。例如,该烷基可取代一个或多个基团,包括但不
限于本发明所述的任选取代的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。“低级烷基”基团是含有1至6个(例如1至4个)碳原子的烷基。
在整个说明书中,“烷基”通常同时指未取代烷基和取代烷基;但是,取代烷基也在本发明中通过确定烷基上的特定取代基来具体地提及。例如,术语“卤化的烷基”或者“卤代烷基”具体是指取代有一个或多个卤素(例如,氟、氯、溴或碘)的烷基。术语“烷氧基烷基”具体是指取代有一个或多个烷氧基的烷基,如下所述。术语“烷基氨基”具体是指取代有一个或多个氨基的烷基,如下所述等。当在一种情况中使用“烷基”而在另一情况中使用具体的术语如“烷基醇”时,不意味着暗示该术语“烷基”不同时指代具体的术语如“烷基醇”等。
这种做法也用于本发明所述的其它基团。也即,当术语如“环烷基”同时指代未取代的和取代的环烷基部分时,该取代的部分可另外具体地在本发明中确定;例如,具体取代的环烷基可称为例如“烷基环烷基”。类似的,取代的烷氧基可具体地称为例如“卤代烷氧基”,具体的取代烯基可为例如“烯醇”等。同样地,使用通用术语如“环烷基”和具体术语如“烷基环烷基”的不意味着该通用术语不同时包含该具体术语。
本发明使用的术语“环烷基”是由至少三个碳原子构成的3至30个碳原子的非芳香族的碳基环。环烷基的例子包括但不限于环丙基、环丁基、环戊基、环己基、环壬基等。术语“杂环烷基”是一类如上定义的环烷基,并且包含在术语“环烷基”的含义中,其中至少一个环碳原子被杂原子例如但不限于氮、氧、硫或磷取代。该环烷基和杂环烷基可为取代或未取代的。该环烷基和杂环烷基可取代有一个或多个基团,包括但不限于如本发明所述的烷基、环烷基、烷氧基、氨基、醚、卤素、羟基、硝基、甲硅烷基、硫-氧代基团和巯基。
本发明使用的术语“聚烯烃基团”是指含有两个或多个彼此相连的CH2基团的基团。“聚烯烃基团”可以表示为—(CH2)a—,其中“a”是2到500之间整数。
本发明使用的术语“烷氧基”和“烷氧基基团”是指通过醚键键合的1至30个碳原子的烷基或环烷基;即“烷氧基”可定义为—OR1,其中R1是如上定义的烷基或环烷基。“烷氧基”也包含刚刚描述的烷氧基聚合物;即烷氧基可为聚醚,如—OR1-OR2或—OR1-(OR2)a-OR3,其中“a”是整数1至500,而R1、R2和R3各自独立地为烷基、环烷基或其组合。
本发明使用的术语“烯基”是2至30个碳原子的烃基,其结构式含有至少一个碳-碳双键。不对称结构如(R1R2)C=C(R3R4)包含E和Z异构体。这可推定在本发明的结构式中,其中存在不对称烯烃,或者它可通过键符号C=C明确表示。该烯基可取代有一个或多个基团,包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环烯基”是非芳香族的3至30个碳原子的碳基环,其由至少3个碳原子构成,并且含有至少一个碳碳双键,即C=C。环烯基的实例包括但不限于环丙烯基、环丁烯基、环戊烯基、环戊二烯基、环己烯基、环己二烯基、环庚烯基等。术语“杂环烯基”是一类如上定义的环烯基,并且包含在术语“环烯基”的含义中,其中该环的至少一个碳原子用杂原子例如但不限于氮、氧、硫或磷取代。环烯基和杂环烯基可为取代或未取代的。该环烯基和杂环烯基可取代有一个或多个基团,包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“炔基”是具有2至30个碳原子的烃基,其结构式至少含有一个碳-碳三键。炔基可为未取代的或者取代有一个或多个基团,所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“环炔基”是非芳香族的碳基环,其包含至少7个碳原子并含有至少一个碳-碳三键。环炔基的实例包括但不限于环庚炔基、环辛炔基、环壬炔基等。术语“杂环炔基”是如上所定义的一种环烯基,并且包含在术语“环炔基”的含义内,其中所述环的碳原子中的至少一个被杂原子替代,所述杂原子例如但不限于氮、氧、硫或磷。环炔基和杂环炔基可为取代或未取代的。环炔基和杂环炔基可取代有一个或多个基团,所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。
本发明使用的术语“芳基”是指含有任何碳基芳香族的60个碳原子及以内的基团,包括但不限于苯、萘、苯基、联苯、苯氧基苯等。术语“芳基”也包括“杂芳基”,其被定义为含有芳香族的基团,所述芳香族基团环内至少含有一个杂原子。杂原子的实例包括但不限于氮、氧、硫或磷。同样,术语“非杂芳基”(其也包括在术语“芳基”中)定义了含有芳香族的基团,所述芳香族基团不含杂原子。芳基可为取代或未取代的。芳基可取代有一个或多个基团,所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛、氨基、羧酸、酯、醚、卤素、羟基、酮、叠氮基、硝基、甲硅烷基、硫-氧代基团或巯基。术语“联芳基”是特定类型的芳基并且包含在“芳基”的定义中。联芳基是指经稠合的环结构结合在一起的两个芳基,如在萘中一样,或者经一个或多个碳-碳键连接的两个芳基,如在联苯中一样。
本发明使用的术语“醛”通过式—C(O)H表示。在整个说明书中,“C(O)”是羰基(即,C=O)的简写形式。
本发明使用的术语“胺”或“氨基”通过式—NR1R2表示,其中R1和R2可以独立的从氢、烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基中选择。
本发明使用的术语“烷基氨基”通过式—NH(-烷基)表示,其中烷基如本发明所述。代表性实例包括但不限于甲基氨基、乙基氨基、丙基氨基、异丙基氨基、丁基氨基、异丁基氨基、仲丁基氨基、叔丁基氨基、戊基氨基、异戊基氨基、叔戊基氨基、己基氨基等。
本发明使用的术语“二烷基氨基”通过式—N(-烷基)2表示,其中烷基如本发明所述。代表性实例包括但不限于二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、二异丁基氨基、二仲丁基氨基、二叔丁基氨基、二戊基氨基、二异戊基氨基、二叔戊基氨基、二己基氨基、N-乙基-N-甲基氨基、N-甲基-N-丙基氨基、N-乙基-N-丙基氨基等。
本发明使用的术语“羧酸”通过式—C(O)OH表示。
本发明使用的术语“酯”通过式—OC(O)R1或者—C(O)OR1表示,其中R1可为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚酯”通过式—(R1O(O)C-R2-C(O)O)a—或者—(R1O(O)C-R2-OC(O))a—表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。术语“聚酯”用于描述通过具有至少两个羧基的化合物与具有至少两个羟基的化合物之间的反应产生的基团。
本发明使用的术语“醚”通过式R1OR2表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“聚醚”通过式—(R1O-R2O)a—表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基并且“a”为1至500的整数。聚醚基团的实例包括聚氧化乙烯、聚氧化丙烯和聚氧化丁烯。
本发明使用的术语“卤素”是指卤素氟、氯、溴和碘。
本发明使用的术语“杂环基”是指单环的和多环的非芳香族环系,并且本发明使用的“杂芳基”是指单环和多环的不多于60个碳原子的芳香族环系:其中环成员中的至少一个不为碳。该术语包括氮杂环丁烷基、
二噁烷基、呋喃基、咪唑基、异噻唑基、异噁唑基、吗啉基、噁唑基(包括1,2,3-噁二唑基、1,2,5-噁二唑基和1,3,4-噁二唑基的噁唑基)、哌嗪基、哌啶基、吡嗪基、吡唑基、哒嗪基、吡啶基、嘧啶基、吡咯基、吡咯烷基、四氢呋喃基、四氢吡喃基、包括1,2,4,5-四嗪基的四嗪基、包括1,2,3,4-四唑基和1,2,4,5-四唑基的四唑基、包括1,2,3-噻二唑基、1,2,5-噻二唑基和1,3,4-噻二唑基的噻二唑基、噻唑基、噻吩基、包括1,3,5-三嗪基和1,2,4-三嗪基的三嗪基、包括1,2,3-***基和1,3,4-***基的***基等。
本发明使用的术语“羟基”通过式—OH表示。
本发明使用的术语“酮”通过式R1C(O)R2表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“叠氮基”通过式—N3表示。
本发明使用的术语“硝基”通过式—NO2表示。
本发明使用的术语“腈”通过式—CN表示。
本发明使用的术语“甲硅烷基”通过式—SiR1R2R3表示,其中R1、R2和R3可独立地为氢或者本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“硫-氧代基团”通过式—S(O)R1、—S(O)2R1、—OS(O)2R1或—OS(O)2OR1表示,其中R1可为氢或者本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。在整个说明书中,“S(O)”为S=O的简写形式。本发明使用的术语“磺酰基”是指通过式—S(O)2R1表示的硫-氧代基团,其中R1可为烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“砜”通过式R1S(O)2R2表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。本发明使用的术语“亚砜”通过式R1S(O)R2表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基或杂芳基。
本发明使用的术语“巯基”通过式—SH表示。
本发明使用的“R1”、“R2”、“R3”、“Rn”(其中n为整数)可独立地具有上面列举的基团中的一个或者多个。例如,如果R1为直链烷基,那么烷基的一个氢原子可任选取代有羟基、烷氧基、烷基、卤素等。取决于选择的基团,第一基团可结合在第二基团内,或者第一基团可侧连(即,连接)至第二基团。例如,对于短语“包含氨基的烷基”,氨基可结合在烷基的主链内。可选择地,氨基可连接至烷基的主链。所选基团的性质将决定是否第一基团嵌入或者连接至第二基团。
本发明所述化合物可含有“任选取代的”部分。通常,术语“取代的”(无论在前面是否存在术语“任选”)意味着指定部分的一个或多个氢被合适的取代基取代。除非另作说明,否则“任选取代的”基团可在基团的每个可取代位置具有合适的取代基,并且当任何给定结构中的一个以上位置可以被选自指定基团的一个以上取代基取代时,取代基可以在每个位置上相同或不同。本发明设想的取代基组合优选为形成稳定的或化学上可行的化合物的组合。还可以设想,在某些方面,除非明确指出相反,各个取代基可进一步任选被取代(即,进一步取代或未取代)。
化合物的结构可通过下式表示:
其被理解为等同于下式:
其中n通常为整数。即,Rn被理解为表示五个单独的取代基Rn(a)、Rn(b)、Rn(c)、Rn(d)、Rn(e)。“单独的取代基”是指每个R取代基可独立地限定。例如,如果在一个情况中Rn(a)为卤素,那么在这种情况下Rn(b)不一定是卤素。
在本发明公开和描述的化学结构和单元中数次提及R1、R2、R3、R4、R5、R6等。在说明书中R1、R2、R3、R4、R5、R6等的任何描述分别适用于引用R1、R2、R3、R4、R5、R6等的任何结构或者单元,除非另作说明。
由于多种原因,使用有机材料的光电子器件变得越来越迫切。用于制造这种装置的许多材料相对便宜,因此有机光电装置具有无机装置成本优势的潜力。此外,有机材料的固有特性,例如它们的柔性,可以使它们非常适合于诸如在柔性基底上的制造等特殊应用。有机光电子器件的实例包括有机发光器件(OLED),有机光电晶体管,有机光伏电池和有机光电探测器。对于OLED,有机材料可能具有优于常规材料的性能优点。例如,有机发光层发光的波长通常可以用适当的掺杂剂容易地调谐。
激子从单重激发态衰减到基态以产生即时发光,其是荧光。如果激子从三重激发态衰减到基态以产生发光,这是磷光。由于重金属原子在单线态和三线态激发态之间的强自旋轨道耦合,有效地增强了系间穿越(ISC),所以磷光金属配合物(如铂配合物)已经表现出其同时利用单线态和三线态激子的潜力,实现100%内部量子效率。因此,磷光金属配合物是有机发光器件(OLED)的发射层中的掺杂剂的良好候选物,并且在学术和工业领域中已经获得了极大的关注。在过去十年中,已经取得了许多成果,从而导致了该技术的有利可图的商业化,例如,OLED已被用于智能手机,电视和数码相机的高级显示器。
然而,迄今为止,蓝色电致发光器件仍然是该技术中最具挑战性的领域,蓝色器件的稳定性是其一大问题。已经证明,主体材料的选择对蓝色器件的稳定性非常重要。但是,蓝色发光材料的三重激发态(T1)最低能量非常高,这意味着蓝色器件的主体材料的三重激发态(T1)最低能量应该更高。这导致蓝色设备的主体材料的开发困难加大。
本发明的金属配合物可以被定制或调谐到期望具有特定发射或吸收特性的特定应用。可以通过改变围绕金属中心的配体的结构或改变配体上的荧光发光体的结构来调节本公开中的金属配合物的光学性质。例如,在发射和吸收光谱中,具有给电子取代基的配体的金属配合物或吸电子取代基通常可以表现出不同的光学性质。可以通过修饰荧光发光体和配体上的共轭基团来调节金属配合物的颜色。
这种本发明的配合物的发射可以例如通过改变配体或荧光发光体结构来调节,例如从紫外线到近红外。荧光发光体是有机分子中的一组原子,其可以吸收能量以产生单重态激发态,单重激子迅速衰变以产生即时发光。一方面,本发明的配合物可提供大部分可见光谱的发射。在具体实例中,本发明的配合物可以在约400nm至约700nm的范围内发光。另一方面,本发明的配合物相对于传统的发射配合物具有改进的稳定性和效率。另外,本发明的配合物可用作例如生物应用,抗癌剂,有机发光二极管(OLED)中的发射体或其组合的发光标记。在另一方面,本发明的配合物可用于发光器件,例如紧凑型荧光灯(CFL),发光二极管(LED),白炽灯及其组合。
本文公开了包含铂的化合物或复合配合物。术语化合物或配合物在本发明可互换使用。另外,本文公开的化合物具有中性电荷。
本文公开的化合物可以表现出期望的性质并且具有可以通过选择合适的配体调节的发射和/或吸收光
谱。在另一方面,本发明可以排除本文具体叙述的任何一种或多种化合物,结构或其部分。
本文公开的化合物适用于各种各样的光学和电光装置,包括但不限于光吸收装置,例如太阳能和感光装置,有机发光二极管(OLED),光发射器件或能够兼容光吸收和发射的器件以及用作生物应用的标记物。
如上所述,所公开的化合物是铂配合物。同时,本文公开的化合物可用作OLED应用的主体材料,例如全色显示器。
本文公开的化合物可用于各种应用。作为发光材料,该化合物可用于有机发光二极管(OLED),发光装置和显示器以及其他发光器件。
本发明的化合物可以使用多种方法制备,包括但不限于本文提供的实施例中所述的那些。
本文公开的化合物可以是延迟的荧光和/或磷光发射体。一方面,本文公开的化合物可以是延迟的荧光发射体。一方面,本文公开的化合物可以是磷光发射体。另一方面,本文公开的化合物可以是延迟荧光发射体和磷光发射体。
以下对本发明的内容进行详细说明。以下所记载的构成要件的说明有时是基于本发明的代表性实施方式或具体例而成,但本发明并不限定于此种实施方式或具体例。
本公开涉及环金属铂配合物,其可用作OLED器件中发光材料和主体材料。
以下实施例向本领域普通技术人员提供如何制造和评价本发明描述的化合物及其OLED器件,所述实施例仅是本公开内容的示范且不圈定限制范围。尽管已经尽力确保关于数值(例如,量、温度等)的准确性,但是应当考虑一些误差和偏差。除非另外说明,否则温度是以℃为单位或者在环境温度下,且压力是在大气压下或附近。
本实施例中所叙述的用于本发明所描述的公开化合物的制备方法是众多方法中的一种,本发明申请公开化合物的制备方法尚有很多其他方法,本申请不圈定限制范围。因此,本公开内容所属颁域的技术人员可容易地修改所叙述的方法或者利用不同的方法来制备所公开的化合物的一种或多种。下列方法仅是示例性的,温度、催化剂、浓度、反应物组成、以及其它工艺条件可改变,并且对于期望的化合物,本公开内容所属领域的技术人员可以容易的选择合适的反应物和条件进行制备。
除非另有说明,以下试验中所涉及到的所有商业试剂购买后直接使用,没有进一步纯化。核磁共振氢谱和碳谱均在氘代氯仿(CDCl3)或氘代二甲基亚砜(DMSO-d6)溶液中测得,氢谱使用400或500兆赫兹的核磁共振谱仪,化学位移以残留溶剂为基准。如果用CDCl3作溶剂,则氢谱以CDCl3(δ=7.26ppm)作为内标。如果用DMSO-d6作溶剂,则氢谱DMSO-d6(δ=2.50ppm)作为内标。以下缩写(或组合)用于解释氢谱峰:s=单峰,d=双重峰,t=三重峰,q=四重峰,p=五重峰,m=多重峰,br=宽峰。
实施例1:四齿环金属铂(II)配合物Pt-17的合成:
(1)中间体QL-CHO的合成:向带有磁力搅拌子的100mL干燥三口瓶中加入tBuQL-Br(2.0g,7.57mmol,1.0当量),3-甲酰基苯硼酸(1.36g,9.09mmol,1.2当量),四三苯基膦钯(175mg,0.15mmol,2mol%)和碳酸钠(1.61g,15.14mmol,2.0当量),抽换氮气三次,在氮气保护下加入甲苯(12mL)、乙醇(10mL)和水(5mL)。将封管置于90℃的油浴锅中搅拌,反应58小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-10:1,得到棕色固体1.97mg,收率90%。1H NMR(500MHz,CDCl3)δ1.47(s,9H),7.42(dd,J=8.0,4.0Hz,1H),7.67(t,J=7.5Hz,1H),7.79(d,J=2.0Hz,1H),7.83(d,J=2.0Hz,1H),7.94(dt,J=7.5,1.5Hz,1H),8.00(dt,J=7.5,1.5Hz,1H),8.20(dd,J=8.5,2.0Hz,1H),8.22(t,J=2.0Hz,1H),8.88(dd,J=4.0,2.0Hz,1H),10.12(s,1H)。
(2)中间体1-Br的合成:向带有磁力搅拌子的反应管中加入QL-CHO(314mg,1.08mmol,1.0当量),NH2-Br(450mg,1.14mmol,1.05当量),焦亚硫酸钠(238mg,1.25mmol,1.1当量)和N,N-二甲基甲酰胺(6mL),该混合物在90℃的油浴中搅拌反应3天,冷却至室温,加入乙酸乙酯稀释,用水洗涤有机相,分液后有机相用无水硫酸钠干燥,过滤后滤液减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-10:1,得到白色固体648mg,收率86%。1H NMR(500MHz,CDCl3)δ1.29(s,9H),1.46(s,9H),6.66–6.68(m,2H),6.97–7.00(m,2H),7.03–7.06(m,1H),7.09(t,J=8.0Hz,1H),7.19(dd,J=8.0,1.0Hz,1H),7.21(dt,J=8.0,1.5Hz,1H),7.24–7.26(m,1H),7.35–7.38(m,2H),7.46–7.51(m,3H),7.54–7.55(m,1H),7.64–7.66(m,2H),7.71(d,J=2.5Hz,1H),8.14(dd,J=8.5,2.0Hz,1H),8.83(dd,J=4.0,2.0Hz,1H)。
(3)中间体1-OMe的合成:向带有磁力转子的封管中加入1-Br(640mg,0.96mmol,1.0当量),1-Bpin(359mg,1.16mmol,1.2当量),四三苯基膦钯(43mg,0.03mmol,3mol%)和碳酸钾(265mg,1.92mmol,2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应41小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-7:1,
得到白色固体724mg,收率98%。1H NMR(500MHz,CDCl3)δ1.31(s,9H),1.42(s,9H),3.86(s,3H),6.66–6.68(m,2H),6.96–6.99(m,2H),7.02–7.06(m,1H),7.10(d,J=8.5Hz,1H),7.13(dt,J=8.0,1.5Hz,1H),7.19–7.25(m,2H),7.27–7.35(m,5H),7.39(d,J=2.5Hz,1H),7.46(dd,J=7.0,1.5Hz,1H),7.49(t,J=2.0Hz,1H),7.54(ddd,J=15.0,8.5,2.5Hz,2H),7.58–7.63(m,5H),7.69(d,J=2.5Hz,1H),7.92(d,J=2.5Hz,1H),8.12(dd,J=8.5,2.0Hz,1H),8.80(dd,J=4.0,2.0Hz,1H)。
(4)配体1-OH的合成:向反应管中依次加入1-OMe(700mg,0.91mmol,1.0当量),吡啶盐酸盐(1.05g,9.11mmol,10当量)和1,3-二甲基-2-咪唑啉酮(3mL)。抽换氮气三次,置于180℃的油浴锅中反应13小时,冷却至室温,碳酸氢钠溶液淬灭,加入乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体634mg,收率92%。1H NMR(500MHz,DMSO-d6)δ1.18(s,9H),1.40(s,9H),6.66–6.69(m,2H),7.01–7.11(m,4H),7.22–7.27(m,3H),7.32–7.39(m,6H),7.48(dd,J=8.5,4.0Hz,1H),7.54(dd,J=8.5,2.5Hz,1H),7.59(dd,J=8.5,2.5Hz,1H),7.61–7.65(m,5H),7.70(d,J=8.5Hz,1H),7.89(d,J=2.0Hz,1H),7.96(d,J=2.5Hz,1H),8.36(dd,J=8.5,2.0Hz,1H),8.70(dd,J=4.0,2.0Hz,1H),10.53(s,1H)。
(5)Pt-17的合成:向带有磁力转子和冷凝管的50mL干燥三口烧瓶中依次加入1-OH(150mg,0.2mmol,1.0当量),氯亚铂酸钾(87mg,0.21mmol,1.05当量),四正丁基溴化铵(6mg,0.02mmol,0.1当量),抽换氮气三次,加入醋酸(15mL),反应液氮气鼓泡30分钟后,室温先搅拌8小时,再在120℃下反应60小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体117mg,收率62%。1H NMR(500MHz,DMSO-d6)δ1.49(s,18H),6.56–6.58(m,1H),7.01(d,J=8.5Hz,1H),7.06(dd,J=8.0,1.0Hz,1H),7.11–7.22(m,7H),7.34–7.43(m,5H),7.56–7.59(m,3H),7.76(d,J=2.5Hz,1H),7.78(d,J=8.5Hz,1H),7.84(dd,J=8.5,2.5Hz,1H),8.02(dd,J=8.0,5.5Hz,1H),8.06(d,J=8.0Hz,1H),8.16(d,J=2.0Hz,1H),8.66(d,J=2.5Hz,1H),8.96(dd,J=8.5,2.0Hz,1H),11.00(dd,J=5.5,1.5Hz,1H)。
实施例2:四齿环金属铂(II)配合物Pt-18的合成:
(1)中间体2-OMe的合成:向带有磁力转子的封管中加入1-Br(1.0当量),2-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和
水(1mL)。将封管置于85℃的油浴锅中搅拌,反应48小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-7:1,得到白色固体,收率约90%。MS:分子量781.37。
(2)配体2-OH的合成:向反应管中依次加入2-OMe(1.0当量),吡啶盐酸盐(10当量)和1,3-二甲基-2-咪唑啉酮(5mL)。抽换氮气三次,置于180℃的油浴锅中反应11小时,冷却至室温,碳酸氢钠溶液淬灭,加入乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体,收率约80%。MS:分子量767.35。
(3)Pt-18的合成:向带有磁力转子的干燥三口烧瓶中依次加入2-OH(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(25mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约50%。MS:分子量960.30。
实施例3:四齿环金属铂(II)配合物Pt-64的合成:
(1)中间体3-OMe的合成:向带有磁力转子的封管中加入3-Br(1.0当量),1-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应48小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-7:1,得到白色固体,收率约85%。MS:分子量560.25。
(2)配体3-OH的合成:向反应管中依次加入3-OMe(1.0当量),吡啶盐酸盐(10当量)和1,3-二甲基-2-咪唑啉酮(6mL)。抽换氮气三次,置于180℃的油浴锅中反应10小时,冷却至室温,碳酸氢钠溶液淬灭,加入乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体,收率约85%。MS:分子量546.23。
(3)Pt-64的合成:向带有磁力转子的干燥三口烧瓶中依次加入3-OH(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(25mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约40%。MS:分子量739.18。
实施例4:四齿环金属铂(II)配合物Pt-104的合成:
(1)中间体1-Cz的合成:向带有磁力转子的封管中加入2-Br(1.0当量),3-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应50小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-7:1,得到白色固体,收率约90%。MS:分子量806.43。
(2)Pt-104的合成:向带有磁力转子的干燥三口烧瓶中依次加入1-Cz(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(25mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约30%。MS:分子量999.38。
实施例5:四齿环金属铂(II)配合物Pt-114的合成:
(1)中间体2-Cz的合成:向带有磁力转子的封管中加入4-Br(1.0当量),3-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应41小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体,收率约80%。MS:分子量559.21。
(3)Pt-114的合成:向带有磁力转子的干燥三口烧瓶中依次加入2-Cz(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(25mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约20%。MS:分子量752.16。
实施例6:四齿环金属铂(II)配合物Pt-113的合成:
(1)中间体3-Cz的合成:向带有磁力转子的封管中加入5-Br(1.0当量),4-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应41小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体,收率约85%。MS:分子量543.23。
(3)Pt-113的合成:向带有磁力转子的干燥三口烧瓶中依次加入3-Cz(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(25mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约30%。MS:分子量736.18。
实施例7:四齿环金属铂(II)配合物Pt-134的合成:
(1)中间体4-OMe的合成:向带有磁力转子的封管中加入6-Br(1.0当量),1-Bpin(1.2当量),四三苯基膦钯(3mol%)和碳酸钾(2.0当量),抽换氮气三次,在氮气保护下加入1,4-二氧六环(6mL)和水(1mL)。将封管置于85℃的油浴锅中搅拌,反应49小时,冷却至室温,水洗,加入乙酸乙酯萃取,水层用乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-7:1,得到白色固体,收率约75%。MS:分子量692.35。
(2)配体4-OH的合成:向反应管中依次加入4-OMe(1.0当量),吡啶盐酸盐(10当量)和1,3-二甲基-2-咪唑啉酮(3mL)。抽换氮气三次,置于180℃的油浴锅中反应12小时,冷却至室温,碳酸氢钠溶液淬灭,加入乙酸乙酯萃取三次,无水硫酸钠干燥,过滤,减压蒸馏除去溶剂。所得粗品用硅胶层析柱
分离提纯,淋洗剂:石油醚/乙酸乙酯=50:1-5:1,得到白色固体,收率约80%。MS:分子量678.34。
(3)Pt-134的合成:向带有磁力转子的干燥三口烧瓶中依次加入4-OH(1.0当量),氯亚铂酸钾(1.05当量),四正丁基溴化铵(0.1当量),抽换氮气三次,加入醋酸(20mL),反应液氮气鼓泡30分钟后,室温先搅拌12小时,再在120℃下反应72小时,冷却至室温,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=1:1-0:1,得到产物黄色固体,收率约20%。MS:分子量871.29。光物理测试和理论计算说明:
使用Horiba Jobin Yvon FluoroLog-3光谱仪上进行稳态发射实验和寿命测量。Pt(II)配合物使用Titan软件包进行理论计算,利用密度泛函理论(DFT)优化了基态(S0)分子的几何结构,使用B3LYP泛函进行DFT计算,其中C、H、O、S和N原子使用6-31G(d)基组,Pt原子使用LANL2DZ基组。
实验数据及分析:
由附图一可知Pt-17可发出强烈的橙红光;其聚甲基丙烯酸甲酯(PMMA)薄膜的量子效率大于80%,可重用做OLED发光层材料。
使用密度泛函理论(DFT)对以下结构进行计算;
表1.DFT理论计算数据
由密度泛函理论(DFT)计算结果(表1、附图2、附图3、附图4)可知,Pt-1、Pt-77、Pt-49、Pt-61、Pt-79、Pt-80、Pt-101、Pt-113和Pt-114具有几乎一样的LUMO轨道分布,LUMO轨道分布主要集中在喹啉上,不同给电子基团对其LUMO轨道分布影响不大。但能级分布会随给电子部分及稠环的改变而改变,从而实现对发光颜色及量子效率的调控。总的来说,密度泛函理论(DFT)计算结果说明了通过调节材料配体上的给电子部分及稠环的结构可以对发光材料的光物理性质进行高效调控。以上实验数据和理论计算结果充分表明,本发明申请中发展的基于8-苯基喹啉衍生物的四齿环金属铂配合物磷光材料具有HOMO和LUMO轨道能级易调、激发态寿命短、磷光量子效率高的特点,表明其在OLED领域有着巨大的应用前景。
器件实施例
本发明的有机发光器件的各层可采用真空蒸镀、溅射、离子电镀等方法,或湿法成膜如旋涂、打印、印刷等方法形成,所用的溶剂没有特别限制。
在本发明的一种优选实施方式中,本发明的OLED器件中含有空穴传输层,空穴传输材料可以优选自已知或未知的材料,特别优选地选自以下结构,但并不代表本发明限于以下结构:
在本发明的一种优选实施方式中,本发明的OLED器件中含有的空穴传输层,其包含一种或多种p型掺杂剂。本发明优选的p型掺杂剂为以下结构,但并不代表本发明限于以下结构:
本发明的一种优选实施方式中,所述的电子传输层可以选自化合物ET-1至ET-13的至少一种,但并不代表本发明限于以下结构:
电子传输层可以有机材料与一种或多种n型掺杂剂(如LiQ)共同形成。
OLED器件实施例:
具体实施底发射OLED器件的结构为在含有ITO的玻璃上,空穴注入层(HIL)为HT-1:P-3(95:5v/v%),厚度为10纳米;空穴传输层(HTL)为HT-1,厚度为90纳米;电子阻挡层(EBL)为HT-10,厚度为10纳米,发光层(EML)为主体材料(RH):本发明铂金属配合物(95:5v/v%),厚度为35纳米,电子传输层(ETL)为ET-13:LiQ(50:50v/v%),厚度为35纳米,然后蒸镀阴极Al为70纳米。主体材料(RH)可选自如下结构:
制作的有机发光器件采用本领域公知的标准方法在10mA/cm2电流条件下测试电压、效率和寿命。
本发明实施例和对比例制备得到的有机发光器件的性能检测结果见表3。
表3
从表3可以看出,上述实施例和对比例中的器件结构除了发光层不同外,其它均一致,基于PtON11Me的器件性能为参考,包含本发明的二价铂金属配合物的器件,相比常规的有机发光器件,电流效率有了显著提高,同时其寿命也有所提高。综上所述,本发明中新型的二价铂金属配合物在有机光电器件上具有较大的应用价值。
本领域的普通技术人员可以理解,上述各实施方式是实现本发明的具体实施例,而在实际应用中,可以在形式上和细节上对其作各种改变,而不偏离本发明的精神和范围。例如,在不背离本发明的精神的情况下,这里描述的许多取代基结构可以用其它结构代替。
Claims (9)
- 金属铂配合物,其结构如通式(1)所示:
其中,Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13、Y14、Y15和Y16各自独立地为CH或N;R1、R2、R3、R4和R5各自独立地为单基取代、双基取代、三基取代、四基取代或者无取代,且R1、R2、R3、R4和R5各自独立地选自氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、硝基、氰基、氨基、单或二烷基氨基、单或二芳基氨基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且两个或者多个邻近的R1、R2、R3、R4和R5各自独立或者选择性连接形成稠环;X为NRa、O或S;其中,Ra为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且可与邻近的R3和R4各自独立或者选择性连接形成稠环;Z为O、S或NRb;其中,Rb为氢、氘、芳基、环烷基、环烯基、杂环基、杂芳基、烷基、烯基、炔基、卤素、羟基、巯基、烷氧基、芳氧基、卤代烷基、酯基、腈基、异腈基、杂芳基、烷氧基羰基、酰氨基、烷氧基羰基氨基、芳氧基羰基氨基、磺酰基氨基、氨磺酰基、氨基甲酰基、烷硫基、亚磺酰基、脲基、磷酰胺基、亚胺基、磺基、羧基、肼基、取代的甲硅烷基、聚合的基团、或其组合;且可与邻近的R1和R5各自独立或者选择性连接形成稠环。 - 根据权利要求1所述的金属铂配合物,其特征在于,所述金属铂配合物为以下结构中的任一者:
- 一种有机发光器件,其特征在于,在基板上具有包含权利要求1或2所述的金属铂配合物的发光层。
- 一种器件,其特征在于,所述器件包含权利要求1或2所述的金属铂配合物。
- 根据权利要求4所述的器件,其特征在于,所述器件为全彩显示器、光伏器件、发光显示器件或有机发光二极管。
- 根据权利要求5所述的器件,其特征在于,包括至少一个阴极、至少一个阳极和至少一层发光层,所述发光层中的至少一层包括权利要求1或2所述的金属铂配合物。
- 根据权利要求6所述的器件,其特征在于,所述器件为有机发光二极管,其发光层中含有所述的金属铂配合物和相应的主体材料,其中金属铂配合物的质量百分数在1%至50%,主体材料没有任何限制。
- 一种显示或照明装置,其特征在于,所述的显示或照明装置含有权利要求4至7所述的器件。
- 根据权利要求1-2任一项所述的金属铂配合物在制作有机光电器件中的应用。
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