CN111788212A - 具有可调发射能的含螺的铂(ii)发射体及其合成 - Google Patents
具有可调发射能的含螺的铂(ii)发射体及其合成 Download PDFInfo
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- CN111788212A CN111788212A CN201980015761.5A CN201980015761A CN111788212A CN 111788212 A CN111788212 A CN 111788212A CN 201980015761 A CN201980015761 A CN 201980015761A CN 111788212 A CN111788212 A CN 111788212A
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- Prior art keywords
- substituted
- aryl
- independently
- unsubstituted
- cycloalkyl
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- 125000003003 spiro group Chemical group 0.000 title claims description 7
- 230000015572 biosynthetic process Effects 0.000 title description 13
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 title description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims description 59
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 58
- 125000000623 heterocyclic group Chemical group 0.000 claims description 48
- -1 nitro, hydroxy Chemical group 0.000 claims description 37
- 125000001072 heteroaryl group Chemical group 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 24
- 125000000304 alkynyl group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000004696 coordination complex Chemical class 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000001301 oxygen Chemical class 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 125000001188 haloalkyl group Chemical group 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical class [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 11
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical class [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical class [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052711 selenium Chemical class 0.000 claims description 9
- 239000011669 selenium Chemical class 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 125000004442 acylamino group Chemical group 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 5
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 150000001638 boron Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 9
- 150000003839 salts Chemical class 0.000 claims 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims 1
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims 1
- YYCNMDBAWNFSBK-UHFFFAOYSA-L dichloroplatinum;methylsulfanylmethane Chemical compound CSC.Cl[Pt]Cl YYCNMDBAWNFSBK-UHFFFAOYSA-L 0.000 claims 1
- KDADQDWVKZJTDQ-UHFFFAOYSA-L methylsulfinylmethane;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].CS(C)=O.CS(C)=O KDADQDWVKZJTDQ-UHFFFAOYSA-L 0.000 claims 1
- 125000005504 styryl group Chemical group 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 238000001429 visible spectrum Methods 0.000 abstract description 4
- 125000005647 linker group Chemical group 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 87
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 238000005160 1H NMR spectroscopy Methods 0.000 description 41
- 125000005842 heteroatom Chemical group 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 34
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 28
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 22
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 18
- 239000012043 crude product Substances 0.000 description 16
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 16
- 238000003818 flash chromatography Methods 0.000 description 16
- 239000000741 silica gel Substances 0.000 description 16
- 229910002027 silica gel Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000003480 eluent Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 11
- 229910000024 caesium carbonate Inorganic materials 0.000 description 11
- 108700003601 dimethylglycine Proteins 0.000 description 11
- 229940078490 n,n-dimethylglycine Drugs 0.000 description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 229910015845 BBr3 Inorganic materials 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
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- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical group C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 125000006574 non-aromatic ring group Chemical group 0.000 description 6
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- 238000006862 quantum yield reaction Methods 0.000 description 6
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- 125000006163 5-membered heteroaryl group Chemical group 0.000 description 5
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- 125000005843 halogen group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- NLLGFYPSWCMUIV-UHFFFAOYSA-N (3-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC(B(O)O)=C1 NLLGFYPSWCMUIV-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- 125000006164 6-membered heteroaryl group Chemical group 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- 239000010949 copper Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
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- 230000009878 intermolecular interaction Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 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
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- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
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Abstract
本申请涉及包含四齿配体的N^C^C^N不对称四齿金属络合物,其具有连接至结合位点的金属,所述结合位点通过三个或四个共价键相互连接,所述共价键可以为单键或双键,且在C^C和C^N部分之间具有桥连接基团。这些连接基团产生具有扭曲的方形平面几何形状的三维金属络合物。四个供体原子配位至金属中心。在与金属结合时,经螯合形成5‑6‑6元的金属环,包括第一氮供体键、第一金属‑碳键、第二金属‑碳键和第二氮供体键。可以通过配体结构在整个可见光谱上对这些金属络合物的光发射进行调节。
Description
背景技术
有机电致发光最初由Gurnee和Reet Teoste在美国专利3,172,862中公开。随后,Tang在美国专利4,356,429和Appl.Phys.Lett.1987,51,12,913中公开了第一种有机发光二极管(OLED)。此后,用于OLED和具有多层设计的OLED器件结构的发光有机材料受到广泛研究。OLED通常优于传统的发光和显示技术,因为其具有更薄的层、更低的工作电压、自发光特性、更高的亮度、更高的色纯度以及其他特征。
基于有机金属材料的器件在器件效率和稳定性方面优于其同等有机器件。铱主导着有机金属OLED行业,因为基于铱(III)的OLED显示出更高的发射效率,更短的发射寿命和良好的器件性能。在铱替代物中,铂是优选的选项,因为其具有更高的自然丰度并且成本比铱低。然而,在OLED生产中,使用铂(II)发射体之前还存在很多问题;这些问题包括效率下降、颜色纯度和颜色可调性。
铂(II)发射体的方形平面配位几何结构固有地显示了导致自淬灭的分子间相互作用,这对OLED器件性能有害,因为高性能迫使保留了高浓度的掺杂剂,从而因分子间相互作用(如三重态-三重态湮灭)导致严重的效率下降。近年来,铂(II)发射体已显示了改善的发射效率,优于其他铂(II)类似物,并且已与铱(III)同等发射体相当(Chem.Sci.2014,5,4819)。这些发射体主要发射绿色至黄色,λem=510-550nm。红色和蓝色铂(II)发射体很少显示出高发射效率和高器件性能,红色固有地具有不匹配的能隙;而蓝色发射体面临的挑战是生产和获得的是较不稳定的器件。因此,需要一种新型材料,其在整个可见光谱(R/G/Y/B色)上显示出发射能,同时具有改善的光发射率和吸收率。
发明内容
本发明的实施方式涉及一种不对称四齿金属络合物发射体,该发射体具有的配体核心使所得的络合物具有高发射效率、最低自淬灭、可调节的发射能和可变发射寿命。所述金属络合物可用作例如显示器的主体材料,并且可充当例如OLED中的发射体。
所述金属络合物发射体具有以下结构:
其中M是Pt,Ir,W,Fe,Ru,Ni,Pd,Cu,Au或Zn;Ar1独立为取代或未取代芳族或杂芳族环,其中X是C或N,其中具有以下结构:以与Ca形成螺单元,其中Ob是键,O,S,NR17,BR17,PR17,CR17R18或SiR17R18,其中Oa是O,S,NR19,BR19,PR19,CR19R20,或SiR19R20,其中N1,N2和N4独立为未取代或取代的硼,碳,氮,氧,硅,锗,磷,硫或硒和n是1-3,其中N3是碳,硼,氮,氧,硅,锗,磷,硫或硒;包含N1,N2,N3和N4的环是饱和的、不饱和的或芳族的环,其中R1是环上的一个或多个取代基并独立为氢,取代或未取代烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,氨基,硝基、羟基,卤素,硫代,烷氧基,卤代烷基,芳基烷基或芳基烯基,其中Ca是碳,硅,或锗,其中R2,R3,R4,R5,R6,R7和R8独立为氢,取代或未取代的烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,氨基,硝基、羟基,卤素,硫代,烷氧基,卤代烷基,芳基烷基或芳基烯基,其中R9,R10,R11,R12,R13,R14,R15和R16独立为氢,卤素,羟基,未取代烷基,取代烷基,环烷基,未取代芳基,取代的芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰基氨基,芳烷基,氰基,羧基,硫代,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基,或烷氧基羰基基团,并且其中一对相邻的R基团可独立形成5-8元芳基或芳基烷基环,所述5-8元芳基或芳基烷基环中可***以下基团中的一个或多个:O,S,N,或NR21;和,其中R17,R18,R19,R20和R21独立为烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,卤代烷基,芳基烷基或芳基烯基。
附图说明
图1显示了具有配体的标号方案的N^C^C^N铂(II)络合物1–10。
图2显示了络合物1、3、4、5、8、9和10在二氯甲烷(2×10-5dm3mol-1)中于室温的紫外-可见光(UV-vis)吸收光谱。
图3显示了络合物1、3、4、5、8、9和10在二氯甲烷(2×10-5dm3mol-1)中于室温的发射光谱。
图4显示了基于络合物1的OLED在不同驱动电压的标准化EL光谱。
图5显示了基于络合物1的OLED的EQE-发光特性。
图6显示了基于络合物4的OLED在不同掺杂浓度的标准化EL光谱。
图7显示了基于络合物4的OLED的EQE-发光特性。
图8A是根据本发明一个实施方式的不对称四齿铂(II)络合物1的分子结构,通过X-射线晶体学测定,显示的为以50%概率水平呈现的椭球,并且为清楚起见去掉了氢。
图8B是根据本发明一个实施方式的络合物1的分子结构,其旋转到一个不同的视角,通过X-射线晶体学测定,显示为以50%概率水平呈现的椭球,并且为清楚起见去掉了氢。
图8C是根据本发明一个实施方式的络合物1的晶体数据、结构解析和精修的表格。
图9显示了根据本发明一个实施方式的1,[2,6-iPrNCN]Cr(THF)2),在CDCl3中的1HNMR光谱,其随温度而变化。
图10是根据本发明一个实施方式的绿色、红色和蓝色发射体(分别为络合物1、络合物4和络合物5)的发射和轨道数据的表格。
图11显示了根据本发明实施方式的不同的Pt(II)不对称络合物。
图12显示了根据本发明实施方式的不同的不对称的含四齿配体的N^C^C^N。
图13显示了根据本发明实施方式的络合物1的化学结构和计算的HOMO、LUMO和优化的T1激发态。
具体实施方式
本发明一个实施方式的是一种含四齿配体的不对称的N^C^C^N。尽管,在本发明的许多实施方式中,尽管两个C结合部位包含碳原子,但两个C部位可为其他原子,如下所示。所述四齿配体具有以下结构:
其中Ar1是取代或未取代芳族或杂芳族环,其中X是N或其他电子对供体;具有以下结构:以与Ca形成螺单元,其中Ca是碳或硅,Ob是键,O,S,NR17,BR17,PR17,CR17R18或SiR17R18,其中Oa是O,S,NR19,BR19,PR19,CR19R20或SiR19R20,其中N1,N2和N4独立为未取代或取代的硼,碳,氮,氧,硅,锗,磷,硫或硒和n是1-3,其中N3是碳,硼,氮,氧,硅,锗,磷,硫或硒;包含N1,N2,N3和N4的环是饱和的、不饱和的或芳族的环,其中R1独立为氢,取代或未取代烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,氨基,硝基,羟基,卤素,硫代,烷氧基,卤代烷基,芳基烷基或芳基烯基,其中R2,R3,R4,R5,R6,R7和R8独立为氢,取代或未取代烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,氨基,硝基、羟基,卤素,硫代,烷氧基,卤代烷基,芳基烷基或芳基烯基,其中R9,R10,R11,R12,R13,R14,R15和R16独立为氢,卤素,羟基,未取代烷基,取代烷基,环烷基,未取代芳基,取代的芳基,酰基,烷氧基,酰氧基,氨基,硝基,酰基氨基,芳烷基,氰基,羧基,硫代,苯乙烯基,氨基羰基,氨基甲酰基,芳氧基羰基,苯氧基羰基,或烷氧基羰基基团和,其中一对相邻的R基团可独立形成5-8元芳基或芳基烷基环,所述5-8元芳基或芳基烷基环中可***以下基团中的一个或多个:O,S,N,或NR21;并且其中R17,R18,R19,R20和R21独立为烷基,烯基,炔基,芳基,杂芳基,环烷基,杂环基,卤代烷基,芳基烷基或芳基烯基。
本发明的另一个实施方式是不对称的含四齿配体的为N^C^C^N的四齿金属络合物。该金属络合物具有以下结构:
在该结构中,结合部位经由3个或4个共价键连接,该共价键可为单或双键。桥连接基团Oa和Ca位于C^C和C^N部分之间。这些Oa和Ca连接基团导致具有扭曲的方形平面几何形状的三维金属络合物。配位至铂(II)中心的4个供体原子构成了Pt-N^C^C^N核心。对于Pt(II),Pd(II),Ru(II),Cu(II)或Zn(II),金属中心具有+2氧化态,或对于Ru(III),Au(III),或Ir(III),金属中心具有+3氧化态。在螯合时形成5-6-6元金属环是因为第一氮供体键,第一金属-碳键,第二金属-碳键和第二氮供体键。
根据本发明实施方式的金属络合物具有良好的热稳定性,在氮气下的分解温度高达430℃。络合物在超过300℃的温度在1x 10-5Torr下升华。根据本发明的一个实施方式,包含络合物的器件通过热沉积法构造,在器件构造后仅留有非常少的残余物。金属络合物在空气中稳定并且可溶于普通的有机溶剂,例如,但不限于,二氯甲烷,氯仿,乙酸乙酯,***,丙酮,己烷,二甲亚砜,二甲基甲酰胺,甲醇和乙醇。这些发射体在有机溶剂中具有良好溶解度,从而有利于使用溶液加工来制造发光器件。
金属发射体显示蓝色、绿色、黄色和红色发射,发射效率几乎为90%。金属发射体可用于发光或显示技术(其中使用单发射体或发射体组合)。在可见光谱(λ=430-700nm)内可调节的发射能通过在配体框架上包含不同的芳族杂环来实现。例如,当被吡啶环取代并且M是Pt(II)时,发生强烈的绿色发射(λem=516±3nm),溶液中的发射量子产率为81%;基于该发射体的器件在很宽的掺杂剂浓度范围(例如,但不限于,1-30wt%)内显示出稳定的绿色发射,CIE坐标为(0.29±0.01,0.60±0.01),其与相位准线(PAL)颜色编码体系中的标准绿色匹配。
除了调节发射能的能力之外,发射寿命可从微秒级变为毫秒级。金属络合物可用作主客体系式发光器件中的发射体或主体。当通过电手段激发时,发射寿命短阻止了该金属发射体经历不理想的电化学反应。发射寿命长的金属络合物更有效地将能量从主体转移到掺杂剂,因为主体材料的自发射是竞争性较小的过程。这些金属络合物显示出浓度增加时最小自淬灭,所显示的自淬灭率常数在107dm3 mol-1s-1量级。伴有5-6-6元金属环形成的配位至金属中心的N^C^C^N核心提供了稳固的主体构造(bulk configuration),得到了具有最小分子间相互作用的高度稳定的发射体。基于该金属发射体的器件显示了宽掺杂窗口,例如但不限于2-30wt%,并且在高达10000cd m-2的高亮度下具有稳定的CIE坐标。
根据本发明实施方式的这些金属络合物的扭曲的方形平面几何形状是如下的示例性络合物的X-射线晶体结构所揭露的独特结构特征:
其如图8A和8B中所示,晶体数据在图8C中给出。图8的示例性络合物具有带有扭曲结构的Pt(II)中心,以使得垂直于C^N 6元环的螺-芴部分投影到螯合金属的表面。该扭曲结构使两个6元环有船样构象,C^C具有氧桥,C^N具有正交的螺-连接基团。在螯合金属上的投影显示出螺-芴单元上的叔丁基的氢原子与Pt(II)中心之间的短距离,或C-H…Pt相互作用。该相互作用导致芴部分的1H NMR信号与相应游离配体的等同信号相比不寻常地偏移。如图9中所示,芴的叔丁基的质子所经历的化学环境在温度升高到373K时合并了;而该络合物上的其他质子在加热时经历了最小的变化,这可归因于络合物的刚性配体骨架。由于根据本发明实施方式的不对称方形平面金属络合物的独特几何形状,调色板是可调节的,如图10中列表的示例性不对称Pt(II)金属络合物所示,其中显示了蓝色、红色和绿色发射。出于该原因,金属络合物是可在可见光发光器件(如OLED)中使用的发射体,当使用多个发射体时,器件可显示对比度,当使用多种发射体时,可以实现全彩显示。可见光发射体能如所设计的那样在如下范围内发射:其中λmax在450nm至635nm上延伸,具有10-7dm3mol-1s-1或更小的自淬灭率常数。发光器件可通过现有技术的方法构造,例如真空沉积或溶液加工。器件可具有延迟的荧光或磷光。
图11显示了根据本发明实施方式的非限制性的不对称四齿金属络合物。这些Pt(II)络合物全都可具有不同的发射光谱,涵盖了各种各样的颜色。通过非限制性不对称四齿配体的结构来限定颜色。
定义
“烷基”是指具有1-6个碳原子的直链或支链的饱和的烃基,其在本文中也称为“低级烷基”。在一些实施方式中,C1-C4烷基是特别优选的。烷基基团的示例包括甲基(C1),乙基(C2),正丙基(C3),异丙基(C3),正丁基(C4),叔丁基(C4),仲丁基(C4),异丁基(C4),正戊基(C5),3-戊基(C5),戊基(C5),新戊基(C5),3-甲基-2-丁基(C5),叔戊基(C5),和正己基(C6)。除非另外指明,每种情况的烷基基团独立为任选取代的,即,未取代(“未取代烷基”)或被一个或多个取代基(例如,如以下情况,1-5个取代基,1-3个取代基,或1个取代基)取代(“取代烷基”)。在某些实施方式中,烷基基团是未取代C1-6烷基(例如,-CH3)。在某些实施方式中,烷基基团是取代的C1-6烷基。
“烯基”是指具有2-6个碳原子直链或支链和一个或多个碳-碳双键(例如,1,2,或3个碳-碳双键)的烃基。一个或多个碳-碳双键可为内部的(例如在2-丁烯中)或末端的(例如在1-丁烯中)。在一些实施方式中,C2-4烯基是特别优选的。烯基基团的示例包括,但不限于,乙烯基(C2),1-丙烯基(C3),2-丙烯基(C3),1-丙烯-2-基(C3),1-丁烯基(C4),2-丁烯基(C4),丁二烯基(C4),戊烯基(C5),戊二烯基(C5),己烯基(C6)等。除非另外指明,每种情况的烯基基团独立为任选取代的,即,未取代(“未取代烯基”)或被一个或多个取代基(例如,如以下情况,1-5个取代基,1-3个取代基,或1个取代基)取代的(“取代烯基”)。在某些实施方式中,烯基基团是未取代C2-6烯基。在某些实施方式中,烯基基团是取代的C2-6烯基。
“炔基”是指具有2-6个碳原子和一个或多个碳-碳叁键(例如,1,2,或3个碳-碳叁键)以及任选的一个或多个碳-碳双键(例如,1,2,或3个碳-碳双键)的直链或支链的烃基。在一些实施方式中,C2-4炔基是特别优选的。在某些实施方式中,炔基不含任何双键。一个或多个碳-碳叁键可为内部的(例如在2-丁炔基中)或末端的(例如在1-丁炔基中)。炔基基团的示例包括但不限于乙炔基(C2),1-丙炔基(C3),2-丙炔基(C3),1-丁炔基(C4),2-丁炔基(C4),戊炔基(C5),3-甲基丁-1-炔基(C5),己炔基(C6)等。除非另外指明,每种情况的炔基基团独立为任选取代的,即,未取代(“未取代炔基”)或被一个或多个取代基(例如,如以下情况,1-5个取代基,1-3个取代基,或1个取代基)取代的(“取代炔基”)。在某些实施方式中,炔基基团是未取代C2-6炔基。在某些实施方式中,炔基基团是取代的C2-6炔基。
"烷氧基"是指基团-OR,其中R是取代或未取代C1-C6烷基基团。在一些实施方式中,C1-C4烷氧基基团是特别优选的。具体的烷氧基基团包括,但不限于,甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,叔丁氧基,仲丁氧基,正戊氧基,正己氧基和1,2-二甲基丁氧基。
"酰基"是指基团-(=O)R,其中R是任选取代的C1-C6烷基。在一些实施方式中,C1-C4烷酰基基团是特别优选的。示例性的C1-C6烷酰基基团包括,但不限于,-(=O)CH3,-(=O)CH2CH3,-(=O)CH2CH2CH3和-(=O)CH(CH3)2。
"卤代"或"卤素"表示氟(F),氯(Cl),溴(Br)和碘(I)。在一些实施方式中,卤代基团是F、-Cl或Br。在一些实施方式中,卤素基团是F或Cl。在一些实施方式中,卤素基团是F。
因此,"卤代烷基"是指被一个或多个卤代基团取代的上述"C1-C6烷基"。在一些实施方式中,C1-C4卤代烷基基团是特别优选的,更优选C1-C2卤代烷基基团。示例性的卤代烷基基团包括,但不限于,-CF3,-CH2F,-CHF2,-CHFCH2F,-CH2CHF2,-CF2CF3,-CCl3,-CH2Cl,-CHCl2、2,2,2-三氟-1,1-二甲基-乙基等。
“环烷基”是指具有3-8个环碳原子和0个杂原子的非芳族环状烃基。在一些实施方式中,C5-C8环烷基是优选的,其是具有5-8个环碳原子和0个杂原子的非芳族环状烃基。在一些实施方式中,C3-C6环烷基是优选的,其是具有3-6个环碳原子和0个杂原子的非芳族环状烃基。在一些实施方式中,C5环烷基是优选的,其是具有5个环碳原子和0个杂原子的非芳族环状烃基。环烷基还包括如下的环体系:其中如上所定义的环烷基环与一个或多个芳基或杂芳基基团稠合,其中连接点在环烷基环上,在这种情况中,碳数继续指定为碳环体系中的碳数。示例性的环烷基基团包括,但不限于,环丙基(C3),环丙烯基(C3),环丁基(C4),环丁烯基(C4),环戊基(C5),环戊烯基(C5),环戊二烯基(C5),环己基(C6),环己烯基(C6),环己二烯基(C6),以及环庚基(C7),环庚烯基(C7),环庚二烯基(C7),环庚三烯基(C7),环辛基(C8),环辛烯基(C8),二环[2.2.1]庚基(C7),二环[2.2.2]辛基(C8)等。除非另外指明,每种情况的环烷基基团独立为任选取代的,即,未取代(“未取代环烷基”)或被一个或多个取代基取代(“取代环烷基”)。在某些实施方式中,环烷基基团是未取代C3-8环烷基。在某些实施方式中,环烷基基团是取代的C3-8环烷基。
“杂环基”是指具有环碳原子和1-3个环杂原子的3-8元非芳族环体系的基团,其中每个杂原子独立选自氮,氧,硫,硼,磷,和硅,其中碳,氮,硫和磷原子可以氧化态存在,例如C(O),S(O),S(O)2,P(O)等。在包含一个或多个氮原子的杂环基基团中,当价位许可时,连接点可为碳或氮原子。在一些实施方式中,4-7元杂环基是优选的,其是具有环碳原子和1-3个环杂原子的4-7元非芳族环体系的基团。在一些实施方式中,5-8元杂环基是优选的,其是具有环碳原子和1-3个环杂原子的5-8元非芳族环体系的基团。在一些实施方式中,4-6元杂环基是优选的,其是具有环碳原子和1-3个环杂原子的4-6元非芳族环体系的基团。在一些实施方式中,5-6元杂环基是优选的,其是具有环碳原子和1-3个环杂原子5-6元非芳族环体系的基团。在一些实施方式中,5元杂环基是更优选的,其是具有环碳原子和1-3个环杂原子的5元非芳族环体系的基团。在一些实施方式中,3-8元杂环基,4-7元杂环基,5-8元杂环基,4-6元杂环基,5-6元杂环基和5元杂环基包含1-3个(更优选1或2个)环杂原子,该环杂原子选自氮,氧和硫(优选氮和氧)。除非另外指明,每种情况的杂环基独立为任选取代的,即,未取代(“未取代杂环基”)或被一个或多个取代基取代(“取代杂环基”)。在某些实施方式中,杂环基基团是未取代3-8元杂环基。在某些实施方式中,杂环基基团是取代的3-8元杂环基。杂环基还包括如下的环体系,其中如上所定义的杂环基环与一个或多个碳环基团稠合,其中连接点在碳环上;或如下的环体系,其中如上所定义的杂环基环与一个或多个芳基或杂芳基基团稠合,其中连接点在杂环基环上;在这种情况中,环成员数继续指定为杂环基环体系中的环成员数。示例性的包含一个杂原子的3元杂环基基团包括,但不限于,氮杂环丙烷基,氧杂环丙烷基,硫杂环丙烷基。示例性的包含一个杂原子的4元杂环基基团包括,但不限于,氮杂环丁烷基,氧杂环丁烷基和硫杂环丁烷基。示例性的包含一个杂原子的5元杂环基基团包括,但不限于,四氢呋喃基,二氢呋喃基,四氢噻吩基,二氢噻吩基,吡咯烷基,二氢吡咯基和吡咯基-2,5-二酮。示例性的包含两个杂原子的5元杂环基基团包括,但不限于,二氧戊环基,氧硫杂环戊烷基,氧硫杂环戊二烯基(1,2-氧硫杂环戊二烯基,1,3-氧硫杂环戊二烯基),二硫杂环戊烷基,二氢吡唑基,二氢咪唑基,二氢噻唑基,二氢异噻唑基,二氢噁唑基,二氢异噁唑基,二氢噁二唑基和噁唑烷-2-酮。示例性的包含3个杂原子的5元杂环基基团包括,但不限于,***啉基,噁二唑啉基,和噻二唑啉基。示例性的包含一个杂原子的6元杂环基基团包括,但不限于,哌啶基,四氢吡喃基,二氢吡啶基,四氢吡啶基,和硫杂环己烷基。示例性的包含两个杂原子的6元杂环基基团包括,但不限于,二氢吡嗪基,哌嗪基,吗啉基,二硫杂环己烷基,二噁烷基。示例性的包含两个杂原子的6元杂环基基团包括,但不限于,三嗪烷基。示例性的包含一个或两个杂原子的7元杂环基基团包括,但不限于,氮杂环庚烷基,二氮杂环庚烷基,氧杂环庚烷基和硫杂环庚烷基。示例性的包含一个或两个杂原子的8元杂环基基团包括,但不限于,氮杂环辛烷基,氧杂环辛烷基,硫杂环辛烷基,八氢环戊烷并[c]吡咯基和八氢吡咯并[3,4-c]吡咯基。示例性的与C6芳环稠合的5元杂环基基团(在本文中也称为5,6-二环杂环基环)包括,但不限于,二氢吲哚基,异二氢吲哚基,二氢苯并呋喃基,二氢苯并噻吩基,苯并噁唑啉酮基等。示例性的与C6芳环稠合的6元杂环基基团(在本文中也称为6,6-二环杂环基环)包括,但不限于,四氢喹啉基,四氢异喹啉基等。“芳基”是指具有在芳族环体系中提供的6-14个环碳原子和0个杂原子的单环或多环(例如,二环或三环)的4n+2芳族环体系(例如,具有在环排列中共享的6、10或14个π电子)。在一些实施方式中,芳基基团具有6个环碳原子(“C6芳基”;例如,苯基)。在一些实施方式中,芳基基团具有10个环碳原子(“C10芳基”;例如,萘基,如1-萘基和2-萘基)。在一些实施方式中,芳基基团具有14个环碳原子(“C14芳基”;例如,蒽基)。“C6-C14芳基”还包括如下的环体系:其中如上所定义的芳环与一个或多个碳环或杂环基基团稠合,其中附接基或连接点在芳环上,在这种情况中,碳原子数继续指定为芳环体系中的碳原子数。典型的芳基基团包括,但不限于,衍生自以下的基团:醋蒽烯(aceanthrylene)、苊烯、醋菲烯(acephenanthrylene)、蒽、薁、苯、六苯并苯、荧蒽、芴、并六苯、萘并四并苯(hexaphene)、hexalene、不对称引达省、对称引达省、茚满、茚、萘、octacene、octaphene、氯甲桥萘(octalene)、卵苯(ovalene)、戊-2,4-二烯、并五苯(pentacene)、并环戊二烯(pentalene)、二苯并菲(pentaphene)、二萘嵌苯(perylene)、非那烯(phenalene)、菲(phenanthrene)、苉(picene)、七曜烯(pleiadene)、嵌二萘(pyrene)、吡蒽(pyranthrene)、玉红省(rubicene)、三亚苯(triphenylene)和三萘(trinaphthalene)。特别地,芳基包括苯基、萘基、茚基和四氢萘基。除非另外说明,芳基的各实例独立地为任选取代的,即,未取代的(“未取代的芳基”)或被一个或多个取代基取代的(“取代的芳基”)。在一些实施方案中,所述芳基为未取代的C6–14芳基。在一些实施方案中,所述芳基为取代的C6–14芳基。
“杂芳基”是指具有在芳族环体系中提供的环碳原子和1-4个环杂原子的5-10元单环或二环4n+2芳族环体系(例如,具有在环排列中共享的6或10个π电子),其中每个杂原子独立选自氮,氧和硫。在一些实施方式中,5元杂芳基是优选的,其是具有环碳原子和1-4环杂原子的5元单环4n+2芳族环体系(例如,具有在环状排列中共享的6个π电子),其中每个杂原子独立选自氮,氧和硫。在包含一个或多个氮原子的杂芳基基团中,当价位允许时,连接点可为碳或氮原子。杂芳基二环环体系可包括位于一个或两个环中的一个或多个杂原子。杂芳基包括如下的环体系:其中如上所定义的杂芳环与一个或多个碳环或杂环基基团稠合,其中连接点是在杂芳环上,在这种情况中,环成员数继续指定为杂芳环体系中的环成员数。除非另外指明,每种情况的杂芳基基团独立为任选取代的,即,未取代(“未取代杂芳基”)或被一个或多个取代基取代(“取代杂芳基”)。在某些实施方式中,杂芳基基团是未取代的5-10元杂芳基。在某些实施方式中,杂芳基基团是取代的5-10元杂芳基。示例性的包含一个杂原子的5元杂芳基基团包括,但不限于,吡咯基,呋喃基和噻吩基。示例性的包含两个杂原子的5元杂芳基基团包括,但不限于,咪唑基,吡唑基,噁唑基,异噁唑基,噻唑基,和异噻唑基。示例性的包含3个杂原子的5元杂芳基基团包括,但不限于,***基,噁二唑基,和噻二唑基。示例性的包含4个杂原子的5元杂芳基基团包括,但不限于,四唑基。示例性的包含一个杂原子的6元杂芳基基团包括,但不限于,吡啶基。示例性的包含两个杂原子的6元杂芳基基团包括,但不限于,哒嗪基,嘧啶基,和吡嗪基。示例性的包含3个或4个杂原子的6元杂芳基基团分别包括,但不限于,三嗪基和四嗪基。示例性的包含一个杂原子的7元杂芳基基团包括,但不限于,氮杂环庚三烯基,氧杂环庚三烯基,和硫杂环庚三烯基。示例性的5,6-二环杂芳基基团包括,但不限于,吲哚基,异吲哚基,吲唑基,苯并***基,苯并噻吩基,异苯并噻吩基,苯并呋喃基,苯并异呋喃基,苯并咪唑基,苯并噁唑基,苯并异噁唑基,苯并噁二唑基,苯并噻唑基,苯并异噻唑基,苯并噻二唑基,吲嗪基,和嘌呤基。示例性的6,6-二环杂芳基基团包括,但不限于,萘啶基,蝶啶基,喹啉基,异喹啉基,噌啉基,喹喔啉基,酞嗪基,和喹唑啉基。
方法和材料
配体和络合物的合成
方案S1.化合物(a)–(y)的合成方案。
方案S2.配体L1–L10的合成方案。
方案S3.络合物1–10的合成方案。
络合物1–10的合成操作。
(a):向烧瓶中装入镁(0.6g,22.8mmol,1.2当量)和2-溴-4,4'-二-叔丁基-1,1'-联苯(7.8g,22.8mmol,1.2当量)。将烧瓶抽真空并用氮气回填。在氮气气氛下向烧瓶中添加60mL无水THF。反应混合物加热回流直到镁完全耗尽,随后冷却至环境温度。将2-(3-溴苯甲酰基)吡啶(5g,19.1mmol,1当量)在30mL无水THF中的溶液于室温在氮气气氛下缓慢添加至上述格氏试剂中。在完全添加后,反应混合物加热回流过夜。减压去除溶剂,随后倒入包含5mL浓H2SO4、5mL乙酸酐和90mL冰乙酸的溶液中。反应混合物于150℃搅拌6小时。混合物随后倒入冷甲醇中。过滤和用冷甲醇洗涤两次之后,获得产物,其是浅黄色固体。产率:6.3g,83%。1H NMR(400MHz,CDCl3):δ 8.72(d,J=5.1Hz,2H),8.04(q,J=8.8Hz,J=7.9Hz,4H),7.90(dt,J=8.0Hz,J=8.0Hz,2H),7.70(d,J=8.0Hz,2H),7.50(dd,J=7.6Hz,J=4.8Hz,2H),7.36(t,J=7.9Hz,2H),1.26(s,tBu,18H)。
一般操作A.N^C-OMe的形成。
在氮气气氛下向烧瓶中装入Pd(PPh3)Cl2(5mol%),K2CO3(3当量),3-甲氧基苯基硼酸(1当量),2-溴吡啶(1当量)和100mL无水甲苯。反应混合物加热回流20小时。在冷却至环境温度之后,混合物用二氯甲烷稀释并用30mL水洗涤3次。合并的有机萃取物用MgSO4干燥,减压浓缩,所得残余物通过快速色谱在硅胶上纯化,提供所需产物。
(b):按照操作A。Pd(PPh3)Cl2(1.2g,1.6mmol,5mol%),K2CO3(13.6g,98.7mmol,3当量),3-甲氧基苯基硼酸(5g,32.9mmol,1当量)和2-溴吡啶(3.1mL,32.9mmol,1当量)。粗产物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(12:1)作为洗脱液以得到产物,其是黄色油状物。产率:5.2g,85%。1H NMR(400MHz,CDCl3):δ 8.68(d,J=4.5Hz,1H),7.76–7.70(m,2H),7.58(s,1H),7.54(d,J=7.7Hz,1H),7.38(t,J=8.0Hz,1H),7.26–7.21(m,1H),6.96(d,J=8.1Hz,1H),3.89(s,3H)。
(c):按照操作A。Pd(PPh3)Cl2(1.1g,1.5mmol,5mol%),K2CO3(21.1g,90.3mmol,3当量),3-甲氧基苯基硼酸(4.7g,30.1mmol,1当量)和2-溴喹啉(5g,30.1mmol,1当量)。粗产物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液以得到产物,其是黄色油状物。产率:6.5g,91%。1H NMR(400MHz,CDCl3):δ 8.19(dd,J=8.7Hz,J=3.5Hz,2H),7.86(d,J=8.6Hz,1H),7.83(d,J=8.1Hz,1H),7.76(d,J=9.3Hz,1H),7.72(t,J=6.2Hz,2H),7.53(t,J=7.8Hz,1H),7.44(t,J=7.9Hz,1H),7.02(dd,J=8.2Hz,J=2.4Hz,1H),3.94(s,3H)。
一般操作B.N^C–OMe的形成
向烧瓶中装入Cu2O(10mol%),在氮气气氛下将KOtBu(2.5当量),3-溴苯甲醚(1当量),1H-吡唑(1当量)和100mL无水DMF添加到烧瓶中。反应混合物加热回流20小时。在冷却至环境温度之后,混合物用二氯甲烷稀释并用30mL水洗涤3次。合并的有机萃取物经MgSO4干燥,减压浓缩,所得残余物通过快速色谱在硅胶上纯化,提供所需产物。
(e):遵循一般操作B。Cu2O(0.84g,5.9mmol,10mol%),KOtBu(16g,146.8mmol,2.5当量),3-溴苯甲醚(7.5mL,58.7mmol,1当量)和1H-吡唑(4g,58.7mmol,1当量)。粗产物通过快速色谱在硅胶上纯化使用己烷/乙酸乙酯(8:2)作为洗脱液,提供所需产物,其是浅棕色油状物。产率:4.1g,40%。1H NMR(400MHz,CDCl3):δ 7.86(d,J=2.4Hz,1H),7.69(s,1H),7.30–7.18(m,3H),6.78(d,J=8.2Hz,1H),6.40(s,1H),3.80(s,3H)。
(f):遵循一般操作B。Cu2O(0.6g,4.0mmol,10mol%),K2CO3(16.7g,120.9mmol,3当量),3-溴苯甲醚(5.1mL,40.3mmol,1当量)和4-叔丁基吡唑(5g,40.3mmol,1当量)。粗产物通过硅胶塞过滤并用二氯甲烷洗涤。将滤液浓缩并不经进一步纯化用于下一步骤。
(g):遵循一般操作B。Cu2O(0.6g,4.0mmol,10mol%),K2CO3(16.7g,120.9mmol,3当量),3-溴苯甲醚(5.1mL,40.3mmol,1当量)和3,5-二甲基吡唑(3.9g,40.3mmol,1当量)。粗产物通过硅胶塞过滤并用二氯甲烷洗涤。将滤液浓缩并不经进一步纯化用于下一步骤。
(d):向烧瓶中装入2-氨基硫代苯酚(5.3mL,49.2mmol,1当量)、3-甲氧基苯甲醛(6mL,49.2mmol,1当量)和偏亚硫酸氢钠(9.4g,49.2mmol,1当量)。添加50mL DMSO以溶解固体,混合物于120℃搅拌1小时。粗产物用二氯甲烷稀释并用50mL水洗涤3次。合并的有机萃取物经MgSO4干燥,减压浓缩,所得残余物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液,提供浅棕色油状物。产率:8.5g,71%.1H NMR(400MHz,CDCl3):δ 8.08(d,J=8.2Hz,1H),7.90(d,J=8.0Hz,1H),7.68(s,1H),7.65(d,J=7.8Hz,1H),7.50(t,J=7.8Hz,1H),7.42–7.38(m,2H),7.05(dd,J=8.2Hz,J=2.2Hz,1H),3.93(s,3H)。
(n):将装有苯乙炔(5mL,45.5mmol,1当量),三甲基甲硅烷基叠氮化物(7.3mL,55.0mmol,1.2当量)和碘化亚铜(I)(88mg,0.46mmol,10mol%)的烧瓶抽真空并充氮气3次。将无水乙醇(50mL)和DMF(50mL)添加至烧瓶,并将混合物回流过夜。粗产物用二氯甲烷稀释并用50mL水洗涤3次。合并的有机萃取物经MgSO4干燥,减压浓缩,所得残余物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1-2:1)作为洗脱液以得到白色固体。产率:3.6g,55%.1H NMR(300MHz,CDCl3):δ 7.38(t,J=7.0Hz,1H),7.46(t,J=7.0Hz,2H),7.83(d,J=7.0Hz,2H),7.98(s,1H)。
(o):向3-溴苯甲醚(5mL,39.5mmol,1当量),三乙胺(22mL,158mmol,4当量),CuI(0.75g,4.0mmol,10mol%)和Pd(PPh3)2Cl2(1.4g,2.0mmol,5mol%)在甲苯(50mL)中的溶液中添加(三甲基甲硅烷基)乙炔(6mL,43.5mmol,1.1当量)。反应混合物于80℃搅拌5小时,随后用EA稀释和用H2O(3x 50mL)洗涤。有机萃取物经MgSO4干燥并减压浓缩。粗产物通过快速柱色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液,得到o,其是无色油状物。产率:6.0g,75%.1H NMR(400MHz,CDCl3):δ 7.20(d,J=8.0Hz,1H),7.06(d,J=8.0Hz,1H),6.99(d,J=6.7Hz,1H),6.87(d,J=8.0Hz,1H),3.75(s,3H),0.19(s,9H)。
(p):向o(6g,29.6mmol,1当量)在MeOH(40mL)中的溶液中添加K2CO3(2g,14.8mmol,0.5当量)。在室温搅拌4小时之后,将混合物用Et2O稀释,并用H2O(3x 50mL)洗涤。有机萃取物经MgSO4干燥并减压浓缩。所得产物为浅黄色油状物,其不经进一步纯化直接用于下一步骤。产率:3.5g,90%.1H NMR(400MHz,CDCl3):δ 7.21(t,J=8.0Hz,1H),7.08(d,J=7.8Hz,1H),7.00(d,J=7.8Hz,1H),6.79(d,J=7.8Hz,1H),3.86(s,3H),3.08(s,1H)。
(j):向包含p(1.63g,13.2mmol,1.5当量),CuSO4·5H2O(0.22g,0.88mmol,0.1当量),和水合肼(0.28mL,8.8mmol,1当量)在乙腈(50mL)中的溶液中添加2-叠氮基-1,3-二甲基苯(1.30g,8.8mmol,1当量)。使混合物于室温在N2气氛下搅拌12小时。混合物随后用二氯甲烷稀释,并用H2O(3x 50mL)洗涤。有机萃取物经MgSO4干燥并减压浓缩。粗产物通过快速柱色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液,得到j,其是无色油状物。产率:1.7g,71%.1H NMR(400MHz,CDCl3):δ 7.93(s,1H),7.64(s,1H),7.51(d,J=6.6Hz,1H),7.43(d,8.0Hz,1H),7.38(s,1H),7.30–7.25(m,2H),7.00–6.95(m,1H),3.96(s,3H,-OMe),2.12(s,6H)。
一般操作C.N^C–OMe的形成
向烧瓶中装入Cu2O(10mol%),1,10-菲咯啉(20mol%),3-溴苯甲醚(1当量),K2CO3(3当量)和2H-1,2,3-***(1.5当量)。将无水DMF(50mL)添加至烧瓶,混合物在氮气气氛下回流48小时。在冷却至室温后,混合物用100mL二氯甲烷稀释,通过硅藻土塞过滤。滤液减压浓缩并通过快速柱色谱在硅胶上进一步纯化,使用正己烷/EA(10:1-8:2)作为洗脱液,得到产物。
(h):遵循一般操作C。2H-1,2,3-***(3g,43.4mmol)和3-溴苯甲醚(3.7mL,29.0mmol)。产率:3.3g,65%。1H NMR(400MHz,CDCl3):δ 7.81(s,2H),7.67(d,J=7.3Hz,2H),7.38(t,J=8.0Hz,1H),6.93–6.88(m,1H),3.89(s,3H)。
(i):遵循一般操作C。n(7.3g,50.0mmol)和3-溴苯甲醚(4.2mL,33.3mmol)。产物不经进一步纯化用于下一步骤。
一般操作D.N^C–OH的形成
在冰浴下向芳基甲基醚(1当量)在30mL无水二氯甲烷中的溶液中缓慢添加BBr3(1M在二氯甲烷中,3当量)。使混合物于室温搅拌2小时。粗混合物缓慢倒入碎冰中,并用饱和Na2CO3溶液中和。有机层用水洗涤两次并用二氯甲烷萃取。减压去除溶剂。粗品通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(7:3)作为洗脱液,提供产物。从正己烷/***混合物重结晶得到白色固体作为产物。
(q):遵循一般操作D。b(1.5g,8.1mmol,1当量)和BBr3(24.3mL,24.3mmol,3当量)。产率:1.0g,73%。1H NMR(400MHz,CDCl3):δ 8.68(d,J=4.2Hz,1H),7.77(t,J=7.2Hz,1H),7.70(d,J=7.9Hz,1H),7.57(s,1H),7.46(d,J=7.7Hz,1H),7.34(t,J=7.9Hz,1H),7.25(s,1H),6.90(d,J=8.0Hz,1H),6.03(s,–OH)。
(r):遵循一般操作D。c(4.0g,17.0mmol,1当量)和BBr3(51.0mL,51.0mmol,3当量)。产率:3.2g,84%。1H NMR(300MHz,CDCl3):δ 8.25–8.17(m,2H),7.87–7.73(m,4H),7.63–7.54(m,2H),7.38(t,J=9.6Hz,1H),6.91(d,J=7.1Hz,1H),6.10(s,–OH)。
(s):遵循一般操作D。d(5.0g,20.6mmol,1当量)和BBr3(61.7mL,61.7mmol,3当量)。产率:3.6g,77%。1H NMR(300MHz,CD3OD):δ 7.95(t,J=8.0Hz,2H),7.54–7.48(m,3H),7.41(t,J=8.1Hz,1H),7.33(t,J=8.1Hz,1H),6.98–6.89(m,1H)。
(t):遵循一般操作D。e(4.2g,24.1mmol,1当量)和BBr3(72.3mL,72.3mmol,3当量)。产率:2.9g,76%。产物不经进一步纯化用于下一步骤。
(u):遵循一般操作D。f(3.5g,15.2mmol,1当量)和BBr3(45.6mL,45.6mmol,3当量)。产率:2.2g,68%。1H NMR(300MHz,CDCl3):δ 8.51(s,–OH),7.62(d,J=7.3Hz,2H),7.26–7.16(m,2H),7.05(d,J=8.0Hz,1H),6.74(d,J=7.2Hz,1H),1.29(s,tbu,9H)。
(v):遵循一般操作D。g(3.5g,15.2mmol,1当量)和BBr3(45.6mL,45.6mmol,3当量)。产率:2.2g,68%。1H NMR(400MHz,CDCl3):δ 7.23(t,J=8.1Hz,1H),7.11(s,1H),6.81–6.75(m,2H),5.99(s,1H),2.31(s,-CH3,3H),2.26(s,-CH3,3H)。
(w):遵循一般操作D。h(3.3g,18.6mmol,1当量)和BBr3(55.9mL,55.9mmol,3当量)。产率:2.1g,70%。1H NMR(300MHz,CDCl3):δ 7.80(s,2H),7.62(d,J=7.8Hz,2H),7.32(t,J=8.2Hz,1H),6.84(dd,J=6.8Hz,1.7Hz,1H),6.53(s,1H)。
(x):遵循一般操作D。i(4g,15.9mmol,1当量)和BBr3(47.8mL,47.8mmol,3当量)。产率:2.8g,75%。1H NMR(400MHz,CDCl3):δ 8.05(s,1H),7.90–7.88(m,2H),7.71(dd,J=8.2Hz,1.9Hz,1H),7.66(s,1H),7.49–7.45(m,2H),7.41–7.33(m,1H),6.83(d,J=6.6Hz,1H),5.39(s,1H)。
(y):遵循一般操作D。j(2.5g,9.0mmol,1当量)和BBr3(26.9mL,26.9mmol,3当量)。产率:1.7g,72%。1H NMR(300MHz,CDCl3):δ 8.16(s,1H),7.29–7.11(m,4H),6.93(d,J=7.9Hz,1H),6.78–6.71(m,2H),1.96(s,6H)。
(k):向烧瓶中装入Pd(PPh3)2Cl2(1.3g,1.8mmol,5mol%),1,5-二溴-2,4-二氟苯(10g,36.8mmol,1当量)和2-(三丁基甲锡烷基)吡啶(11.9mL,36.8mmol,1当量)。将烧瓶抽真空并用氮气回填。在氮气气氛下添加80mL无水甲苯,混合物加热回流过夜。粗混合物通过少量硅藻土过滤,随后减压浓缩。粗产物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(15:1)作为洗脱液以得到产物,其是黄色固体。产率:7.4g,75%。1H NMR(400MHz,CDCl3):δ 8.63(d,J=4.8Hz,1H),8.21(t,J=8.0Hz,1H),7.68(s,2H),7.25–7.19(m,1H),6.91(t,J=9.4Hz,1H);19F NMR(376MHz,CDCl3):δ=–102.62,–113.78.
(l):向烧瓶中装入Pd(dppf)Cl2(2g,2.5mmol,10mol%),NaOAc(7.3g,73.6mmol,3当量),二(频哪醇化合)二硼烷(9.5g,36.8mmol,1.5当量)和化合物k(6.6g,24.5mmol,1当量)。将烧瓶抽真空并用氮回填。在氮气气氛下添加100mL无水1,4-二噁烷,混合物加热回流过夜。粗混合物通过少量硅藻土过滤,随后减压浓缩。粗产物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液以得到产物,其是浅黄色固体。产率:4.7g,60%。1H NMR(400MHz,CDCl3):δ 8.72(d,J=4.6Hz,1H),8.34(t,J=8.2Hz,1H),7.77–7.69(m,2H),7.30–7.24(m,1H),6.88(t,J=10.1Hz,1H),1.60(s,12H);19F NMR(376MHz,CDCl3):δ=–98.41,–108.81.
(m):向烧瓶中装入化合物l(2g,6.3mmol,1当量),添加40mL二氯甲烷以溶解固体。添加20mL 30%(w/w)(10当量)H2O2,并使混合物于室温搅拌过夜。粗产物用二氯甲烷稀释并用50mL水洗涤3次。合并的有机萃取物经MgSO4干燥,减压浓缩,所得残余物通过快速色谱在硅胶上纯化,使用正己烷/乙酸乙酯(10:1)作为洗脱液,提供浅棕色固体。产率:0.8g,65%。1HNMR(400MHz,CDCl3):δ 8.69(d,J=4.7Hz,1H),8.48(s,–OH),7.80(t,J=7.7Hz,1H),7.72(d,J=8.1Hz,1H),7.54(t,J=8.6Hz,1H),7.31(t,J=6.2Hz,1H),6.89(t,J=10.3Hz,1H);19F NMR(376MHz,CDCl3):δ=–124.41,–133.16.
一般操作E。配体合成
向烧瓶中装入CuI(10mol%),Cs2CO3(3当量),N,N-二甲基甘氨酸(30mol%),芳基醇(1当量)和a(1当量)。将烧瓶抽真空并用氮气回填。在氮气气氛下向烧瓶中添加100mL无水1,4-二噁烷或无水DMSO。混合物于150℃搅拌2–3天。过滤除去固体,滤液用水洗涤3次,用二氯甲烷萃取,随后用MgSO4干燥。混合物浓缩并通过快速色谱纯化,使用正己烷/乙酸乙酯作为洗脱液以得到所需产物。
(L1):遵循一般操作E。CuI(0.06g,0.3mmol,10mol%),Cs2CO3(2.9g,8.8mmol,3当量),N,N-二甲基甘氨酸(0.09g,0.9mmol,30mol%),化合物q(0.5g,2.9mmol,1当量)和化合物a(1.5g,2.9mmol,1当量)。产率:0.71g,41%。1H NMR(500MHz,CDCl3):δ 8.66(m,2H,H1,H23),7.70(t,J=7.1Hz,1H,H3),7.70(d,J=8.2Hz,1H,H9),7.67–7.58(m,6H,H28,H25,H17,H4),7.42–7.32(m,4H,H27,H21,H8),7.22(dt,J=2.1Hz,J=6.5Hz,1H,H2),7.20(t,J=8.1Hz,1H,H14),7.15(t,J=7.5Hz,1H,H22),6.96–6.92(m,2H,H20,H7),6.84–6.79(m,3H,H15,H13,H11),1.27(s,18H,tBu)。
(L2):遵循一般操作E。CuI(0.92g,0.2mmol,5mol%),Cs2CO3(3.2g,9.7mmol,2当量),N,N-二甲基甘氨酸(1.0g,1.4mmol,30mol%),化合物m(1.0g,4.8mmol,1当量)和化合物a(2.5g,4.8mmol,1当量)。产率:1.9g,61%。1H NMR(600MHz,CDCl3):δ 8.64(d,J=4.4Hz,1H,H1),8.64(d,J=6.2Hz,1H,H23),7.77–7.69(m,3H,H8,H4,H3),7.61(d,J=8.0Hz,2H,H28),7.58(s,2H,H25),7.40(t,J=7.5Hz,1H,H21),7.37(d,8.0Hz,2H,H27),7.22(t,J=5.6Hz,1H,H2),7.14(t,J=7.9Hz,1H,H14),7.07(t,J=5.2Hz,1H,H22),6.96–6.92(m,2H,H20,H17),6.79–6.74(m,3H,H15,H13,H11),1.26(s,18H,tBu)。19F NMR(376MHz,CDCl3):δ–115.36,–125.14.
(L3):遵循一般操作E。CuI(0.05g,0.2mmol,10mol%),Cs2CO3(2.2g,6.6mmol,3当量),N,N-二甲基甘氨酸(0.07g,0.7mmol,30mol%),化合物s(0.5g,2.2mmol,1当量)和化合物a(1.1g,2.2mmol,1当量)。产率:0.5g,37%。1H NMR(500MHz,CDCl3):δ 8.70(d,J=4.1Hz,1H,H25),8.05(d,J=8.0Hz,1H,H2),7.86(d,J=8.0Hz,1H,H5),7.74(d,J=6.1Hz,1H,H11),7.71(s,1H,H13),7.63–7.59(m,3H,H27,H15),7.46(t,J=7.9Hz,1H,H3),7.44–7.32(m,6H,H29,H23,H17,H10,H4),7.20(t,J=8.1Hz,1H,H16),7.08–7.01(m,2H,H24,H9),6.93(d,J=7.9Hz,1H,H22),6.88–6.82(m,3H,H30,H19),1.26(s,18H,tBu)。
(L4):遵循一般操作E。CuI(0.04g,0.2mmol,10mol%),Cs2CO3(1.9g,2.2mmol,3当量),N,N-二甲基甘氨酸(0.1g,0.7mmol,30mol%),化合物r(0.5g,2.3mmol,1当量)和化合物a(1.2g,2.3mmol,1当量)。产率:0.66g,44%。1H NMR(500MHz,CDCl3):δ 8.65(d,J=4.5Hz,1H,H27),8.14(t,J=6.7Hz,2H,H7,H2),7.84(d,J=5.2Hz,1H,H11),7.80–7.74(m,3H,H15,H8,H5),7.69(t,J=7.0Hz,1H,H4),7.63–7.61(m,4H,H32,H29),7.49(t,J=6.9Hz,1H,H3),7.39–7.35(m,4H,H31,H25,H12),7.19–7.15(m,1H,H18),7.04–6.98(m,2H,H26,H13),6.92(d,J=8.0Hz,1H,H24),6.88–6.86(m,2H,H21,H17),6.81(d,J=7.9Hz,1H,H19),1.26(s,18H,tBu)。
(L5):遵循一般操作E。CuI(0.06g,0.3mmol,10mol%),Cs2CO3(3.0g,9.3mmol,3当量),N,N-二甲基甘氨酸(0.1g,0.9mmol,30mol%),化合物t(0.5g,3.1mmol,1当量)和化合物a(1.6g,3.1mmol,1当量)。产率:0.9g,51%。1H NMR(600MHz,CDCl3):δ 8.70(d,J=5.7Hz,1H,H21),7.83(s,1H,H1),7.69–7.67(m,5H,H26,H23,H3),7.44–7.36(m,5H,H25,H19,H15,H5),7.30(t,J=8.1Hz,1H,H6),7.24(t,J=4.4Hz,1H,H12),7.08–7.05(m,1H,H20),6.98(d,J=8.1Hz,1H,H18),6.91–6.89(m,3H,H13,H11,H9),6.83(d,J=8.2Hz,1H,H7),6.42(s,1H,H2),1.33(s,18H,tBu)。
(L6):遵循一般操作E。CuI(0.06g,0.3mmol,10mol%),Cs2CO3(3.0g,9.3mmol,3当量),N,N-二甲基甘氨酸(0.1g,0.9mmol,30mol%),化合物u(0.5g,3.1mmol,1当量)和化合物a(1.6g,3.1mmol,1当量)。产率:1.1g,55%。1H NMR(600MHz,CDCl3):δ 8.65(d,J=4.6Hz,1H,H21),7.64–7.58(m,6H,H26,H23,H3,H1),7.41–7.36(m,4H,H25,H19,H5),7.30–7.25(m,2H,H9,H6),7.18(t,J=8.3Hz,1H,H12),7.06(dt,J=6.1Hz,J=2.4Hz,1H,H20),6.91(d,J=7.9Hz,1H,H18),6.85–6.81(m,3H,H15,H13,H11),6.75(d,J=8.1Hz,1H,H7),1.30(s,9H,tBu),1.27(s,18H,tBu)。
(L7):遵循一般操作E。CuI(0.06g,0.3mmol,10mol%),Cs2CO3(3.0g,9.3mmol,3当量),N,N-二甲基甘氨酸(0.1g,0.9mmol,30mol%),化合物v(0.6g,3.1mmol,1当量)和化合物a(1.6g,3.1mmol,1当量)。产率:0.90g,47%。1H NMR(500MHz,CDCl3):δ 8.67(d,J=4.6Hz,1H,H21),7.67–7.63(m,4H,H26,H23),7.43–7.40(m,3H,H25,H19),7.30(t,J=8.1Hz1H,H6),7.19(t,J=8.3Hz,1H,H12),7.13(d,J=7.2Hz,1H,H5),7.10–7.05(m,1H,H20),7.05(s,1H,H9),6.94(d,J=8.0Hz,1H,H18),6.89–6.84(m,4H,H15,H13,H11),5.97(s,1H,H2),2.29(s,3H,-CH3),2.22(s,3H,-CH3),1.31(s,18H,tBu)。
(L8):遵循一般操作E。CuI(0.18g,0.93mmol,10mol%),Cs2CO3(9.1g,27.9mmol,3当量),N,N-二甲基甘氨酸(0.30g,2.8mmol,30mol%),化合物w(1.5g,9.3mmol,1当量)和化合物a(4.7g,9.3mmol,1当量)。产率:2.2g,40%。1H NMR(600MHz,CD2Cl2):δ 8.64-8.63(m,1H,H14),7.80(s,1H,H1),7.76(d,J=8.1Hz,1H,H6),7.66(d,J=6.9Hz,3H,H25,H25‘,H20),7.61(s,3H,H22,H22‘,H2),7.46(dt,J=7.7Hz,1.9Hz,1H,H11),7.42(dd,J=8.0Hz,1.9Hz,2H,H24,H24‘),7.37(t,J=8.1Hz,1H,H5),7.23(t,J=8.0Hz,1H,H18),7.13–7.11(m,1H,H10),6.99(d,J=7.9Hz,1H,H12),6.93-6.89(m,2H,H19,H4),6.86-6.84(m,2H,H17,H8),1.29(s,18H,tBu)。
(L9):遵循一般操作E。CuI(0.16g,0.84mmol,10mol%),Cs2CO3(8.2g,25.2mmol,3当量),N,N-二甲基甘氨酸(0.26g,2.5mmol,30mol%),化合物x(2.0g,8.4mmol,1当量)和化合物a(4.3g,8.4mmol,1当量)。产率:2.1g,37%。由于纯化中的困难,粗产物不经进一步纯化用于下一步骤。
(L10):遵循一般操作E。CuI(0.09g,0.49mmol,10mol%),Cs2CO3(4.8g,14.7mmol,3当量),N,N-二甲基甘氨酸(0.15g,1.5mmol,30mol%),化合物y(1.3g,4.9mmol,1当量)和化合物a(2.5g,4.9mmol,1当量)。产率:0.92g,27%。由于纯化中的困难,粗产物不经进一步纯化用于下一步骤。1H NMR(400MHz,CDCl3):δ 8.65(d,J=4.0Hz,1H),7.78(s,1H),7.69(d,J=8.2Hz,1H),7.62–7.61(m,3H),7.51–7.31(m,7H),7.21–7.18(m,3H),7.09(m,1H),7.05–7.02(m,1H),6.94(d,J=8.0Hz,1H),6.92–6.84(m,3H)。
铂(II)络合物(1–10)的合成
所有络合物均通过K2PtCl4(1.2当量)、相应配体(1当量)和催化量的nBu4NCl在100mL回流冰乙酸中反应24小时来制备。蒸馏去除溶剂,粗品用水洗涤两次,用二氯甲烷萃取。有机层经MgSO4干燥,浓缩和通过快速色谱纯化,使用正己烷/乙酸乙酯(8:2至6:4)作为洗脱液以得到白色至橙黄色固体。
(1):L1(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.5g,62%。1H NMR(600MHz,CDCl3):δ 10.13(s,1H,H25),9.06(d,J=5.4Hz,1H,H23),8.24(d,J=5.3Hz,1H,H1),7.99(d,J=8.1Hz,1H,H4),7.92(t,J=7.9Hz,1H,H3),7.77(d,J=8.0Hz,1H,H28),7.60–7.52(m,5H,H27,H25‘,H21,H9,H7),7.29–7.16(m,6H,H28‘,H27‘,H22,H13,H8,H2),7.02(d,J=8.4Hz,1H,H20),6.79(t,J=7.8Hz,1H,H14),6.58(d,J=7.8Hz,1H,H13),1.40(s,9H,tBu),0.77(s,9H,tBu)。MS(FAB):793.3[M+]。C43H38N2OPt·0.5CH3COOC2H5的分析计算:C64.50,H 5.05,N 3.34。实测:C 64.32,H4.72,N 3.53.
(2):L2(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.3g,37%。1H NMR(600MHz,CD2Cl2):δ 9.97(s,1H,H25),9.05(d,J=6.4Hz,1H,H23),8.33(d,J=4.8Hz,1H,H4),8.23(d,J=5.0Hz,1H,H1),7.98(t,J=7.9Hz,1H,H3),7.81(d,J=8.0Hz,H28),7.68–7.63(m,2H,H27,H21),7.56(d,J=7.7Hz,1H,H28‘),7.52(s,1H,H25‘),7.37(t,J=5.9Hz,1H,H22),7.25–7.16(m,3H,H27‘,H13,H2),7.05(d,J=8.3Hz,1H,H20),6.83–6.76(m,2H,H14,H8),6.52(d,J=7.2Hz,1H,H15),1.40(s,9H,tBu),0.75(s,9H,tBu)。19F NMR(376MHz,CDCl3):δ-118.38,-127.05。13C NMR(150MHz,CD2Cl2):δ 162.98,162.94,154.41,152.27,151.64,151.11,150.87,149.89,148.24,143.10,139.70,138.99,138.60,137.66,137.63,136.98,134.05,126.94,126.12,125.61,125.52,124.86,124.58,124.50,124.08,123.96,123.17,121.52,78.09,71.93,66.23,35.57,35.20,31.85,31.15,30.24。MS(FAB):829.2[M+]。C43H36F2N2OPt·0.5H2O的分析计算:C 61.57,H 4.45,N 3.34。实测:C 61.49,H 4.09,N3.50.
(3):L3(0.7g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.6g,77%。1H NMR(600MHz,CD2Cl2):δ 10.32(s,1H,H27),9.23(d,J=5.5Hz,1H,H25),7.98(d,J=8.0Hz,1H,H2),7.84(d,J=7.9Hz,1H,H30),7.66–7.54(m,5H,H30‘,H29,H27‘,H23,H11),7.34(t,J=7.3Hz,1H,H3),7.26(t,J=7.6Hz,1H,H10),7.25–7.22(m,1H,H29‘),7.17(t,J=7.0Hz,1H,H24),7.16–7.10(m,3H,H22,H9,H4),7.07(d,J=6.7Hz,1H,H15),6.90(d,J=8.4Hz,1H,H5),6.77(t,J=6.9Hz,1H,H16),6.53(d,J=7.8Hz,1H,H17),1.41(s,9H,tBu),0.66(s,9H,tBu)。13C NMR(150MHz,CD2Cl2)δ 181.13,162.67,154.83,154.39,153.10,151.47,151.32,150.85,150.54,150.09,142.95,139.72,138.85,137.14,133.78,128.92,127.17,127.13,126.07,125.69,125.64,125.50,124.94,124.59,124.21,123.41,123.15,121.62,121.12,120.86,120.25,119.62,118.90,117.39,116.57,77.51,34.99,34.66,31.55,31.28,30.40,22.62,13.85。MS(FAB):851.3[M+]。C45H40N2OPt的分析计算:C 63.44,H 4.73,N3.29。实测:C 63.72,H 4.53,N 3.50.
(4):L4(0.7g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.5g,54%。1H NMR(600MHz,CDCl3):δ 10.38(s,1H,H29),8.68(d,J=5.3Hz,1H,H27),8.37(d,J=8.7Hz,1H,H7),8.20(d,J=8.7Hz,1H,H8),7.83(t,J=7.7Hz,2H,H32,H5),7.75(d,J=7.6Hz,1H,H11),7.63–7.60(m,2H,H31,H4),7.55(s,1H,H29‘),7.48(t,J=6.8Hz,1H,H25),7.34–7.18(m,6H,H32‘,H31',H17,H13,H3,H2),7.02(d,J=8.4Hz,1H,H24),6.91(t,J=7.4Hz,1H,H12),6.86–6.82(m,2H,H26,H18),6.66(d,J=7.6Hz,1H,H19),1.40(s,9H,tBu),0.67(s,9H,tBu)。13C NMR(150MHz,CDCl3)δ 166.36,161.78,153.72,153.52,152.51,151.09,150.68,149.55,147.85,146.22,141.69,139.46,138.42,137.24,136.45,129.27,128.79,128.38,128.13,127.59,126.58,125.87,125.26,124.71,124.41,124.10,123.86,122.53,120.78,120.29,119.57,119.07,118.29,117.82,116.92,115.94,76.69,76.67,76.64,76.63,76.61,71.48,31.62,30.83。MS(FAB):843.3[M+]。C47H40N2OPt·0.5H2O的分析计算:C66.18,H 4.85,N 3.28。实测:C 66.27,H 4.71,N 3.50.
(5):L5(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.6g,72%。1H NMR(500MHz,C6D6):δ 9.61–9.01(宽峰,1H,H23),8.95(d,J=5.6Hz,1H,H21),7.78(d,J=8Hz,2H,H26,H5),7.53(d,J=3.3Hz,1H,H11),7.52(s,1H,H3),7.48–7.44(m,2H,H25,H6),7.28–7.22(m,3H,H13,H7,H1),7.04–6.92(m,4H,H26‘,H25‘,H18,H12),6.71(t,J=6.9Hz,1H,H19),6.39(t,J=6.9Hz,1H,H20),6.27(s,1H,H23‘),6.12(s,1H,H2),1.18(s,18H,tBu)。13CNMR(150MHz,C6D6)δ 204.19,163.12,156.09,155.58,152.41,151.74,151.22,146.76,142.72,138.03,137.31,126.52,126.40,125.68,125.51,125.00,124.63,123.26,121.67,119.99,119.16,117.57,116.36,114.61,107.09,105.85,81.28,71.94,34.77,31.09。MS(FAB):783.3.3[M+H+]。C41H37N3Opt的分析计算:C 62.90,H 4.76,N 5.37。实测:C 62.99,H4.81,N 5.54.
(6):L6(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.6g,67%。1H NMR(600MHz,CDCl3):δ 9.20(d,J=4.2Hz,1H,H21),9.17–8.86(宽峰,1H,H23),7.95(s,1H,H1),7.63–7.60(m,2H,H26,H23‘),7.58(t,J=7.2Hz,1H,H19),7.39–7.25(m,5H,H26‘,H25,H25‘,H20,H3),7.17(t,J=7.9Hz,1H,H6),7.12(d,J=7.8Hz,1H,H11),7.08(d,J=7.7Hz,1H,H5),7.01–6.99(m,2H,H18,H7),6.78(t,J=7。9Hz,1H,H12),6.57(d,J=6.8Hz,1H,H13),2.17(s,9H,tBu),1.23(s,18H,tBu)。13C NMR(150MHz,CDCl3)δ 207.03,162.14,154.99,154.35,151.84,150.49,149.96,146.16,142.01,137.46,135.17,134.70,125.72,125.16,124.92,124.28,123.61,123.28,122.45,120.83,119.17,118.36,116.18,114.64,113.06,105.09,76.98,76.77,71.55,53.39,35.03,31.51,31.32,30.91,29.85。MS(FAB):739.3[M+H+]。C45H45N3OPt·0.5CHCl3的分析计算:C 60.81,H 5.10,N 4.68。实测:C 60.72,H 5.29,N4.75.
(7):L7(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.53g,65%。1H NMR(500MHz,CDCl3):δ 10.27(s,1H,H23),9.34(d,J=4.3Hz,1H,H21),7.77(d,J=8.0Hz,1H,H26),7.57(t,J=8.4Hz,2H,H26‘,H25),7.50–7.46(m,2H,H23‘,H19),7.23(d,J=8.0Hz,1H,H25‘),7.20–7.16(m,2H,H7,H5),7.10–7.07(m,3H,H20,H11,H6),7.01(d,J=5.9Hz,1H,H18),6.75(t,J=7.9Hz,1H,H12),6.53(d,J=6.7Hz,1H,H13),6.05(s,1H,H2),2.76(s,3H,-CH3),1.87(s,3H,-CH3),1.37(s,9H,tBu),0.90(s,9H,tBu)。13C NMR(150MHz,CDCl3)δ162.37,154.59,154.39,151.39,151.18,150.45,150.10,148.24,142.57,141.47,139.81,138.25,137.14,127.06,125.98,125.67,125.63,124.80,124.47,123.82,122.87,121.33,121.20,120.16,120.00,119.64,116.09,115.33,112.81,110.48,107.98,78.11,71.90,54.80,54.69,35.56,31.88,31.74,31.43,15.15,14.88。MS(FAB):811.2[M+H+]。C43H41N3OPt的分析计算:C 63.69,H 5.10,N 5.18。实测:C 63.70,H 5.10,N 5.13.
(8):L8(0.6g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.31g,40%。1H NMR(500MHz,CDCl3):δ 9.17(s,1H,H20),8.78(br,2H,H22),8.00(s,1H,H1),7.69–7.64(m,4H,H2,H19,H25,H25‘),7.58(d,J=7.8Hz,1H,H4),7.42(d,J=7.5Hz,2H,H24,H24‘),7.34–7.32(m,1H,H18),7.27(t,J=7.9Hz,1H,H5),7.08(d,J=8.0Hz,2H,H6,H10),7.02(d,J=8.2Hz,1H,H17),6.78(t,J=7.9Hz,1H,H11),6.52(d,J=7.9Hz,1H,H12),1.56(s,18H,tBu)。13C NMR(150MHz,CD2Cl2)162.50,154.95,153.87,152.18,151.39,150.43,145.30,142.90,138.78,138.21,135.62,133.04,125.83,125.78,125.36,124.59,124.42,121.27,120.00,116.93,116.50,115.29,113.77,109.06,54.36,54.18,53.99,53.91,53.71,53.64,35.50,31.64,31.57,31.47,31.44,31.17。C40H36N4OPt的分析计算:C 61.29,H 4.63,N 7.15。实测:C 61.31,H 4.74,N 7.19.
(9):L9(0.7g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.36g,42%。1H NMR(500MHz,CD2Cl2):δ 9.25(d,J=5.6Hz,1H,H26),8.81(br,2H,H28,H28‘),7.92-7.91(m,3H,H8,H31,H31'),7.70-7.65(m,4H,H1,H4,H10,H24),7.52(t,J=7.2Hz,2H,H5,H7),7.46(d,J=7.3Hz,1H,H6),7.42(d,J=7.9Hz,2H,H30,H30‘),7.37(t,J=7.1Hz,1H,H25),7.32-7.28(m,1H,H11),7.11-7.09(m,2H,H12,H16),7.04(d,J=8.2Hz,1H,H23),6.79(t,J=7.9Hz,1H,H17),6.54(d,J=7.7Hz,1H,H18),1.12(s,18H,tBu)。13C NMR(150MHz,CD2Cl2)δ162.57,155.03,153.90,152.27,151.42,150.44,149.15,145.30,142.92,138.76,138.25,129.99,129.73,129.64,126.58,125.83,125.45,124.64,124.54,121.31,120.02,116.96,116.67,115.27,113.96,109.14,78.11,71.99,55.60,54.78,54.43,54.22,53.57,35.51,32.16,31.57,23.22,14.44。C46H40N4OPt·1/3H2O的分析计算:C 63.80,H 4.73,N 6.47。实测:C 63.83,H 4.72,N 6.55.
(10):L10(0.7g,1.0mmol,1当量)和K2PtCl4(0.5g,1.2mmol,1.2当量)。产率:0.31g,35%。1H NMR(600MHz,CDCl3):δ 9.49(d,J=5.7Hz,1H,H25),8.95(br,2H,H27,H27‘),7.84(s,1H,H1),7.62(d,J=7.9Hz,2H,H30,H30‘),7.45(t,J=6.9Hz,1H,H23),7.38-7.35(m,3H,H5,H29,H29‘),7.32(d,J=7.2Hz,1H,H11),7.23-7.16(m,4H,H4,H6,H10,H15),7.12-7.09(m,2H,H9,H24),6.92(d,J=8.1Hz,1H,H22),6.80(t,J=7.8Hz,1H,H16),6.60(d,J=7.8Hz,1H,H17),2.12(s,6H,-CH3),1.17(s,18H,tBu)。13C NMR(150MHz,CDCl3)δ 161.33,156.79,155.05,153.92,153.52,150.32,150.29,142.73,137.72,137.28,137.12,135.88,135.34,130.61,128.75,125.82,125.41,124.90,124.65,124.46,123.77,122.90,120.47,119.35,119.12,117.36,116.27,116.19,115.68,77.02,76.81,71.55,60.42,35.06,31.52,31.50,31.44,31.39,21.07,17.68,14.20。C48H44N4OPt·0.5CHCl3的分析计算:C 61.47,H 4.73,N5.91。实测:C 61.71,H 4.89,N 5.83.
络合物的光物理、电化学数据和热降解温度
a在脱气CH2Cl2溶液(2×10–5mol dm–3)中测定。bτobs=发射寿命。c发射量子产率使用在0.1M硫酸中的硫酸奎宁作为标准品(Φem=0.546)来估算。d发射量子产率使用在脱气苯中的BPEA(9,10-二(苯基乙炔基)蒽)作为标准品(Φem=0.85)来估算。e发射量子产率使用在脱气CH3CN中的[Ru(bpy)3](PF6)2(bpy=2,2'-联吡啶)作为标准品(Φem=0.062)来估算。f5wt%在PMMA薄膜中;使用Hamamatsu C11347 QY绝对PL量子产率测量***来确定。g5wt%在mCP薄膜中;使用Hamamatsu C11347 QY绝对PL量子产率测量***测定。h从氧化/还原波开始时估算,使用真空度之下4.8eV的Cp2Fe+/0值。i从在热重分析中络合物具有5%总失重的温度开始估算。
X-射线衍射分析
在Bruker X8 Proteum衍射仪上收集单晶体的X-射线衍射数据。整合衍射强度以及图像,并使用程序SAINT解读。通过直接法采用SHELXS-97程序解析晶体结构,并通过全矩阵最小二乘法使用程序SHELXL-97来精修。如图8中所示,Pt(II)中心适应于高度扭曲的方形平面几何形状,并且迫使螺-芴投影到包含吡啶的螯合环的表面上。
发射器件的构造
构造具有如下结构的发绿光器件:ITO/HAT-cn(5nm)/TAPC(50nm)/TCTA(10nm)/TCTA:26DczPPy:发射体(15nm)/TMPYPB(50nm)/LiF(1.2nm)/Al(150nm)。
以类似方式,构造具有如下结构的发红光器件:ITO/HAT-cn(5nm)/TAPC(50nm)/TCTA(10nm)/TCTA:26DczPPy:发射体(15nm)/TMPYPB(50nm)/LiF(1.2nm)/Al(150nm)。
构造具有如下结构的发天蓝色光的器件:ITO/MoOx/TAPC/TCTA/发射体:CzSi/TSPO1/TPBI/LiF/Al。
构造具有如下结构的发黄光器件:ITO/MoOx/TAPC/TCTA/发射体:CzSi/TSPO1/TPBI/LiF/Al.
金属发射体的理论计算
包含四齿配体的不对称N^C^C^N中的不同芳族环Ar1实现了对所得Pt(II)络合物的最低吸收能量进行调整,并且在可见光谱中大范围地发射从蓝色到红色的颜色。使用DFT/TDDFT方法对1进行了理论计算。计算的最低吸收能(对应于S0→S1跃迁)在优化的基态几何形状时为415nm。计算值与426nm的实验值良好吻合。这一吸收带主要来自HOMO→LUMO的跃迁,如图13所示,HOMO主要位于Pt(II)离子和四齿配体的氧连接基的两个苯基环上。如图13所示,LUMO在C^N片段上被离域化,而芴基-吡啶部分的贡献很小。如图13所示,最低三重态激发态(T1)的进一步优化揭示了T1激发态主要由三重态配体内电荷转移(3ILCT)性质所主导,导致垂直发射能经计算为569nm。用优化的T1几何形状计算出的辐射衰减率(kr)是1.97x 105s-1,很好地与1.42x 105s-1的经验估算kr相当。
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应当理解,本文描述的实施例和实施方案仅用于说明目的,本领域技术人员根据所述实施例和实施方案会想到对本发明进行修饰或改变,这些修饰和改变都包括在本发明的精神和范围内。
Claims (17)
1.一种不对称金属络合物,包括以下结构:
其中M是Pt、Ir、W、Fe、Ru、Ni、Pd、Cu、Au或Zn,其中Ar1是取代或未取代芳族或杂芳族环,其中X是N或其他电子对供体;是并与Ca形成螺单元,其中Ca是桥接原子并可独立为例如,氮、碳、硼、磷、硅、硫或其组合,Ob是键、O、S、NR17、BR17、PR17、CR17R18或SiR17R18,其中Oa是O、S、NR19、BR19、PR19、CR19R20或SiR19R20,其中N1、N2和N4独立为未取代或取代的硼、碳、氮、氧、硅、锗、磷、硫或硒,n是1-3,其中N3是碳、硼、氮、氧、硅、磷、硫或硒;包含N1、N2、N3和N4的环是饱和、不饱和或芳族的环,其中R1独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷或芳基烯基,其中R2、R3、R4、R5、R6、R7和R8独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷基或芳基烯基,其中R9、R10、R11、R12、R13、R14、R15和R16独立为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代的芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羰基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基基团,和其中一对相邻的R基团可独立形成5-8元芳基或芳基烷基环,所述5-8元芳基或芳基烷基环中可***以下基团中的一个或多个:O、S、N或NR21;其中R17、R18、R19、R20和R21独立为烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、卤代烷基、芳基烷基或芳基烯基。
2.根据权利要求1所述的金属络合物,其中Ar1是芳族环或杂芳族环,其可为取代或未取代的;其中X配位至中心金属原子M;优选地,Ar1是任选取代的杂芳族环,其中X是N,并且取代基独立选自烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、卤代烷基、芳基烷基或芳基烯基,并且所有取代基任选被以下取代:烷基、烯基或炔基。
3.根据权利要求1或2所述的金属络合物,其中N1、N2和N4独立为硼、碳、氮、氧、硅、锗、磷、硫或硒;其中N3独立为配位至中心金属原子M的碳;包含N1、N2、N3和N4的环是饱和的、不饱和的或芳族的环;其中R1独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷基或芳基烯基;其中n和m中的每个独立为整数1、2或3;优选地,包含N1、N2、N3和N4的环是芳基。
5.根据权利要求1-4中任一项所述的金属络合物,其中M是Pt。
6.根据权利要求1-5中任一项所述的金属络合物,其中R2-R8独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷基或芳基烯基。
7.根据权利要求1-6中任一项所述的金属络合物,其中Ca可独立为氮、碳、硼、磷、硅、氧、硫或其组合。
9.一种四齿配体,其包括以下结构:
其中Ar1是取代或未取代芳族或杂芳族环,其中X是N或其他电子对供体;是并与Ca形成螺单元,其中Ca是碳或硅,Ob是键、O、S、NR17、BR17、PR17、CR17R18、或SiR17R18、其中Oa是O、S、NR19、BR19、PR19、CR19R20或SiR19R20,其中N1、N2和N4独立为未取代或取代的硼、碳、氮、氧、硅、锗、磷、硫或硒和n是1-3,其中N3是碳、硼、氮、氧、硅、锗、磷、硫或硒;包含N1、N2、N3和N4的环是饱和的、不饱和的或芳族的环,其中R1独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷基或芳基烯基,其中R2、R3、R4、R5、R6、R7和R8独立为氢、取代或未取代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、氨基、硝基、羟基、卤素、硫代、烷氧基、卤代烷基、芳基烷基或芳基烯基,其中R9、R10、R11、R12、R13、R14、R15和R16独立为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代的芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基基团,和其中一对相邻的R基团可独立形成5-8元芳基或芳基烷基环,所述5-8元芳基或芳基烷基环中可***以下基团中的一个或多个:O、S、N、或NR21;和其中R17、R18、R19、R20和R21独立为烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环基、卤代烷基、芳基烷基或芳基烯基。
11.一种制备金属络合物的方法,包括:
提供根据权利要求9或10的四齿配体;
提供包含Pt、Ir、W、Fe、Ru、Ni、Pd、Cu、Au或Zn的金属盐;和
将四齿配体与金属盐反应。
13.根据权利要求12所述的方法,其中金属盐是四氯铂(II)酸钾、双二甲基硫醚二氯化铂(II)、顺式二氯双(二甲亚砜)铂(II)、二氯(1,5-环辛二烯)铂(II)或四氯铂酸钾(II)。
14.根据权利要求12或13所述的方法,其中反应是在溶剂中回流。
15.根据权利要求14所述的方法,其中溶剂是乙酸或乙酸与氯仿或二氯甲烷的混合物。
16.一种发光器件,包含根据权利要求1-8中任一项所述的至少一种金属络合物。
17.根据权利要求16所述的发光器件,其中所述器件包括至少一种有机发光二极管(OLED)。
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