CN110272453B - Tridentate phosphine ligand with dimethyl thiophene skeleton, synthetic method thereof, copper complex thereof, synthetic method of copper complex thereof and application of copper complex - Google Patents
Tridentate phosphine ligand with dimethyl thiophene skeleton, synthetic method thereof, copper complex thereof, synthetic method of copper complex thereof and application of copper complex Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003446 ligand Substances 0.000 title claims abstract description 63
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 39
- BZYUMXXOAYSFOW-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical group CC=1C=CSC=1C BZYUMXXOAYSFOW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000004699 copper complex Chemical class 0.000 title abstract description 15
- 238000010189 synthetic method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000004820 halides Chemical class 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003111 delayed effect Effects 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- -1 [3- (2, 5-dimethyl-4-bromothienyl) ] phenylphosphine Chemical compound 0.000 description 6
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004776 molecular orbital Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- NWYUIYYDNDZXBK-UHFFFAOYSA-N 3,4-dibromo-2,5-dimethylthiophene Chemical compound CC=1SC(C)=C(Br)C=1Br NWYUIYYDNDZXBK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical compound PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 241001131927 Placea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- LGDAGYXJBDILKZ-UHFFFAOYSA-N [2-methyl-1,1-dioxo-3-(pyridin-2-ylcarbamoyl)-1$l^{6},2-benzothiazin-4-yl] 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 LGDAGYXJBDILKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- UVXZPMQTSDNCGZ-UHFFFAOYSA-N diphenyl-[1-(2-phosphanylphenyl)cyclohexa-2,4-dien-1-yl]phosphane Chemical compound C1C=CC=CC1(C2=CC=CC=C2P)P(C3=CC=CC=C3)C4=CC=CC=C4 UVXZPMQTSDNCGZ-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HPEUEJRPDGMIMY-IFQPEPLCSA-N molybdopterin Chemical compound O([C@H]1N2)[C@H](COP(O)(O)=O)C(S)=C(S)[C@@H]1NC1=C2N=C(N)NC1=O HPEUEJRPDGMIMY-IFQPEPLCSA-N 0.000 description 1
- 238000004646 natural bond orbital Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention belongs to the technical field of copper complexes, and particularly relates to a tridentate phosphine ligand based on a dimethylthiophene skeleton, a synthetic method of the tridentate phosphine ligand, a copper complex of the tridentate phosphine ligand, a synthetic method of the copper complex, and a synthetic method and application of the copper complex of the tridentate phosphine ligand. The mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton can emit strong yellow green light, has high thermal decomposition temperature and high thermal stability, and is suitable for serving as an OLED luminescent material.
Description
Technical Field
The invention belongs to the technical field of copper complexes, and particularly relates to a tridentate phosphine ligand based on a dimethylthiophene skeleton, a synthetic method of the tridentate phosphine ligand, a copper complex of the tridentate phosphine ligand, a synthetic method of the copper complex, and a synthetic method and application of the copper complex of the tridentate phosphine ligand.
Background
In the last few years, luminescent materials have gained attention for their application in OLEDs and optoelectronic devices. In general, noble metal complexes such as iridium and platinum complexes, which typically exhibit rapid intersystem crossing (ISC) and high quantum efficiency and short lifetimes due to noble metal center-induced high spin-orbit coupling (SOC) effects. Theoretically, these complexes can make full use of singlet and triplet excitons, thereby achieving 100% quantum efficiency. However, the high price of these noble metals is a great disadvantage, which also limits their application in photovoltaic materials to a great extent.
Because of the advantages of abundant photophysical properties, low cost, abundant reserves and the like, the cuprous complex is one of the most promising photoelectric materials at present. In recent years, there have been some reports of the use of cationic cu (i) complexes as light emitting materials, in particular complexes based on mixed ligands of α, α' -diimine and triphenylphosphine, having high quantum efficiency. However, the presence of counter anions makes the complexes unsuitable for sublimation and vapor deposition, making it difficult to obtain high efficiency OLEDs. Neutral Cu (I) complexes with good thermal stability are suitable for obtaining high-efficiency OLEDs by vapor deposition, Volz and the like report that neutral Cu (I) complexes with External Quantum Efficiency (EQE) reaching 23% in 2015, and the luminous efficiency can be comparable with that of noble metal complexes.
At present, there are few reports of green and yellow light-emitting neutral cu (i) complexes, and the quantum efficiency is yet to be further improved. This is because the complex loses a large amount of energy when excited due to the Jahn-Teller effect caused by structural distortion or the like. Therefore, how to increase the rigidity of the molecule is the key to increase the quantum efficiency of the complex.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a tridentate phosphine ligand based on a dimethylthiophene skeleton, a synthetic method of the tridentate phosphine ligand, a copper complex of the tridentate phosphine ligand, a synthetic method of the copper complex, and a synthetic method and application of the copper complex of the tridentate phosphine ligand.
The technical scheme provided by the invention is as follows:
a tridentate phosphine ligand based on a dimethylthiophene skeleton, which has the following structural formula:
in the technical scheme, the thiophene group is of an electron-rich heterocyclic structure and can be used as an electron donor part. The whole tridentate phosphine ligand based on the dimethylthiophene skeleton has a tridentate chelating triphosphin ligand structure, so that the structural rigidity of the complex can be enhanced, and the luminous efficiency of the complex can be improved.
The invention also provides a synthetic method of the tridentate phosphine ligand based on the dimethylthiophene skeleton, which comprises the following steps:
based on the technical scheme, the tridentate phosphine ligand based on the dimethyl thiophene skeleton can be obtained by synthesizing the existing raw material short-circuit line, and the yield is high, the condition temperature is high, and the process is simple.
The invention also provides application of the tridentate phosphine ligand based on the dimethylthiophene skeleton, which is provided by the invention and is used as a ligand.
The tridentate phosphine ligand based on the dimethylthiophene skeleton has a tridentate chelating triphosphine ligand structure, and the thiophene group contained in the tridentate chelating triphosphine ligand has an electron-rich heterocyclic structure and can be used as an electron donor part, so that the structural rigidity of the complex can be integrally enhanced, the luminous efficiency of the complex is improved, and the tridentate phosphine ligand is suitable for being used as a ligand.
The invention also provides a mononuclear four-coordination cuprous halide complex of tridentate phosphine ligand based on a dimethylthiophene skeleton, which has the following structural general formula:
wherein X is I, Br or Cl.
In the technical scheme, the mononuclear four-coordination cuprous halide complex based on the tridentate phosphine ligand of the dimethylthiophene skeleton can emit strong yellow green light, has a thermal decomposition temperature close to 400 ℃, is high in thermal stability, and is suitable for serving as an OLED luminescent material.
The invention also provides a synthesis method of the mononuclear four-coordination cuprous halide complex based on the tridentate phosphine ligand of the dimethylthiophene skeleton, which comprises the following steps:
wherein X is I, Br or Cl.
Based on the technical scheme, the mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethyl thiophene skeleton can be obtained by synthesizing the existing raw material short-circuit line, and has the advantages of high yield, temperature and process simplicity.
The invention also provides application of the mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton as a fluorescent material.
The mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton can emit strong yellow-green fluorescence and can be used as a fluorescent material.
Further, the fluorescent material can be used as a heat activation delayed fluorescent material.
The mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton has a thermal activation delayed fluorescence effect and can be used as a thermal activation delayed fluorescence material.
Further, the fluorescent material is used as a yellow-green fluorescent material.
The mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton can emit strong yellow-green fluorescence and can be used as a yellow-green fluorescence material.
The invention also provides application of the mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton as an organic light-emitting diode material.
The mononuclear four-coordination cuprous halide complex of the tridentate phosphine ligand based on the dimethylthiophene skeleton can emit strong yellow green light, has the thermal decomposition temperature close to 400 ℃, has high thermal stability, and is suitable for serving as an organic light-emitting diode material.
The invention also provides an OLED device, which at least comprises an organic light-emitting layer, wherein the material of the organic light-emitting layer is selected from any one or more of the complexes provided by the claim 4.
The OLED device provided by the invention can emit yellow green light, and has high brightness and high external quantum efficiency.
Drawings
FIG. 1 shows DTBr2 in CDCl31H NMR spectrum in (1).
FIG. 2 shows ligand DTTP in CDCl3In (1)1H NMR spectrum.
FIG. 3 shows the reaction of Complex 1 in CDCl3In (1)1H NMR spectrum.
FIG. 4 shows complex 2 in CDCl3In (1)1H NMR spectrum.
FIG. 5 shows complex 3 in CDCl3In (1)1H NMR spectrum.
FIG. 6 shows DTBr2 in CDCl3In (1)31P NMR spectrum.
FIG. 7 shows ligand DTTP in CDCl3In (1)31P NMR spectrum.
FIG. 8 shows the reaction of Complex 1 in CDCl3In (1)31P NMR spectrum.
FIG. 9 shows complex 2 in CDCl3In (1)31P NMR spectrum.
FIG. 10 shows complex 3 in CDCl3In (1)31P NMR spectrum.
FIG. 11 is an ORTEP diagram of complexes 1-3.
FIG. 12 shows the IR spectra of ligand DTTP and complexes 1-3.
FIG. 13.298K Complex 1-3 and DTTP in CH2Cl2Absorption spectrum of (1).
FIG. 14. complexes 1-3 in CH2Cl2Front line molecular orbital electron cloud distribution.
FIG. 15 shows that complexes 1 to 3 are in CH2Cl2Front line molecular orbital electron cloud distribution.
FIG. 16. complexes 1-3 in CH2Cl2Front line molecular orbital electron cloud distribution.
FIG. 17 shows complex 1 in CH2Cl2Absorption spectrum of (1).
FIG. 18 shows complex 2 in CH2Cl2Absorption spectrum of (1).
FIG. 19 shows complex 3 in CH2Cl2Absorption spectrum of (1).
FIG. 20 is normalized emission spectra of complexes 1-3 in the solid state (a)293K and (b) 77K.
FIG. 21 is a CIE diagram of complexes 1-3.
FIG. 22 HOMO and LUMO electron cloud profiles in complexes 1-3.
FIG. 23 TGA curves for complexes 1-3.
FIG. 24 is a graph of device performance, wherein (a) is an EQE-luminance graph, (b) is an EL graph and a CIE graph based on the EL graph, (c) is a CD-CE graph, and (d) is a PE-luminance graph.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
1.1 instruments and reagents
Reagent: all reagents were commercially available and analytically pure. Tetrahydrofuran was used before water was re-evaporated over sodium wire under nitrogen atmosphere and benzophenone was used as indicator. 3, 4-dibromo-2, 5-dimethylthiophene was synthesized according to the literature. The instrument comprises the following steps: the infrared spectrum was obtained by means of a Nicolet iS10 FTIR Fourier transform infrared spectrometer (KBr pellet),1H,13c and31p NMR spectra were obtained using a Varian 600 MHz NMR spectrometer using deuterium-loaded reagent lock fields and references, chemical shifts were measured in ppm and H spectra were measured in SiMe4As a standard, the phosphorus spectrum is 85% H3PO4Is a standard. The high resolution mass spectrum was analyzed by a Bruker Autoflex MALDI-TOF mass spectrometer, and the elemental analysis of C and H was performed by a Vario Micro Cube elemental analyzer. The single crystal structure of the complex 1-3 adopts a Bruker APEX DUO diffractometer. The ultraviolet visible spectrum adopts a Unicam He lambda ios alpha spectrometer, and the photoluminescence spectrum adopts an FLS920 steady-state and time-resolved fluorescence spectrometer. The solid state quantum efficiency is measured by using a Hamamatsu system and an integrating sphere. Thermogravimetric analysis A Perkin-Elmer Diamond TG/DTA thermal analyzer was used.
1.2 Synthesis of the complexes
The synthetic route of the complex is shown below.
1.2.1 Synthesis of bis [3- (2, 5-dimethyl-4-bromothienyl) ] phenylphosphine (DTBr2)
2, 5-dimethyl-3, 4-dibromothiophene (6.00g,22.22mmol) was dissolved in 90mL Et2The O solution was cooled to-78 deg.C, 9.33mL (23.33mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise, the mixture was stirred for 1.5h, and dichlorophenylphosphine (2.07g,11.56mmol) in Et was added2O solution (10mL), stirring was continued for 0.5h then the solution was gradually warmed to room temperature and dichloromethane was added to the mixture. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give a crude productAnd separated by column chromatography (eluent: petroleum ether: dichloromethane ═ 1:4) to give 4.38g of a white solid in 80.8% yield.1H NMR(600MHz,CDCl3)δ:7.44-7.37(m,2H),7.35-7.30(m,3H),2.35(s,6H),1.97(s,6H).31P NMR(240MHz,CDCl3),δ＝-25.13.
1.2.2 Synthesis of bis [3- (2, 5-dimethyl-4-diphenylphosphinothiophenyl) ] phenylphosphine (DTTP)
Bis [3- (2, 5-dimethyl-4-bromothienyl)]Phenylphosphine (4.00g,8.19mmol) was dissolved in 60mL of THF, cooled to-78 deg.C, 7.9mL (19.75mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise, stirred for 1h, a solution of diphenylphosphine chloride (4.36g,19.75mmol) in THF (5mL) was added and stirring was continued for 0.5h, after which the solution was gradually warmed to room temperature and dichloromethane was added to the mixture. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give a crude product, which was isolated by column chromatography (eluent: petroleum ether: acetone ═ 24:1) to give 3.89g of a white solid in 68.0% yield.1H NMR(500MHz,CDCl3)δ:7.44-7.39(m,2H),7.24-7.14(m,19H),7.09-7.04(m,4H)，1.94(s,6H),1.74(s,6H).13C NMR(125MHz,CDCl3),δ＝133.51,133.34,132.28,132.12,131.89,128.09,128.04,127.97,127.88,127.88,127.78,127.31,127.27,15.77,15.08.31P NMR(200MHz,CDCl3),δ＝-23.89(2P)[J(P-P)＝140Hz],-28.87(1P)[J(P-P)＝139Hz].MS(ESI):m/z calcd for C42H37P3S2,699.1583,found:699.1514.Anal.Calcd for C42H37P3S2:C,72.19；H,5.34,found:C,72.23；H,5.33.
1.2.3 Synthesis of complexes 1-3
(1) Synthesis of Complex 1
Cuprous iodide (0.27g,1.43mmol) was added to 30mL CH containing DTTP (1.00g,1.43mmol)2Cl2To the solution, the mixture was stirred at room temperature for 12 hours, the reaction mixture was filtered, the solvent was removed under reduced pressure to give a yellow powder, and the powder was dissolved in a mixed solvent of dichloromethane and THF to be recrystallized to give yellow crystals (1.14g, 89.8%).1H NMR(600MHz,CDCl3)δ:7.77-7.72(m,4H),7.32-7.27(m,3H),7.25-7.13(m,14H),7.08-7.03(m,4H),2.03(s,6H),1.58(s,6H).31P NMR(240M,CDCl3)δ:-19.99,-41.79.MS(MALDI-TOF):m/z calcd for[C42H37CuIP3S2+H]+,890.0002,found:890.1330.Anal.Calcd for C42H37CuIP3S2:C,56.73；H,4.19,found:C,56.71；H,4.20.
(2) Synthesis of Complex 2
Synthesis procedure for Complex 2 referring to the synthesis of Complex 1, cuprous bromide (0.21g, 1.43mmol) was used instead of cuprous iodide to give 1.01g of pale yellow crystals with 83.5% yield.1H NMR(600MHz,CDCl3)δ:7.80-7.75(m,4H),7.29-7.27(m,2H),7.25-7.12(m,15H),7.03-6.99(m,4H),2.03(s,6H),1.59(s,6H).31P NMR(240MHz,CDCl3)δ:-18.62,-41.64.MS(MALDI-TOF):m/z calcd for[C42H37CuBrP3S2+H]+,843.0087,found:843.0256.Anal.Calcd for C42H37CuBrP3S2:C,59.89；H,4.43；found:C,59.87；H,4.44.
(3) Synthesis of Complex 3
Synthesis of Complex 3 referring to the synthesis of Complex 1, cuprous chloride (0.14g, 1.43mmol) was used instead of cuprous iodide to give 0.97g of colorless crystals with a yield of 85.1%.1H NMR(600MHz,CDCl3)δ:7.80-7.75(m,4H),7.25-7.10(m,17H),7.02-6.97(m,4H),2.04(s,6H),1.61(s,6H).31P NMR(240MHz,CDCl3)δ:-17.87,-40.80.MS(MALDI-TOF):m/z calcd for[C42H37CuClP3S2+H]+,798.0646,found:798.0578.Anal.Calcd for C42H37CuClP3S2:C,63.23；H,4.67；found:C,63.25；H,4.66.
2 results and analysis
2.1 Nuclear magnetic map
2.1.1 nuclear magnetic resonance hydrogen spectroscopy
In FIGS. 1 to 5, bis [3- (2, 5-dimethyl-4-bromothienyl)]Method for preparing phenylphosphine DTBr2, ligand DTTP and complex 1-3 in deuterated chloroform1And H NMR spectrum, wherein chemical shift, integral and peak split conditions are consistent with the structure.
2.1.2 31P NMR spectra
FIGS. 6-10 are nuclear magnetic phosphorus spectra of DTBr2, ligand DTTP and complex 1-3 in deuterated chloroform. The chemical shift of phosphorus in DTBr2 was-25.13 and was a single peak, consistent with the actual structure. The nuclear magnetic phosphorus spectrum of ligand DTTP has 2 groups of signal peaks, the chemical shift is-28.87, and the P is connected with 2 thiophene rings, because the electron-rich property of thiophene causes the electron cloud density on P to increase, and the P is positioned in a high field region. The left and right peaks with chemical shifts of-28.19 and-29.58, respectively, are the coupling peaks of the adjacent 2P pairs of P, and the calculated coupling constant J (P-P) ═ 139 Hz. Chemical shift-23.89 is 2 PPh2The-24.59 peak is the coupling peak of P to 2 thiophene rings, the calculated coupling constant is J (P-P) ═ 140Hz, which indicates that DTTP ligand structure is symmetrical, and 2 PPh2The ratio of the integrated area of the peak P to the integrated area of P with 2 thiophene rings attached is 2: 1.
The nuclear magnetic phosphorus spectrogram of the complex 1-3 has two groups of signal peaks, and the chemical shifts of the complex are respectively-19.99 and-41.79; 18.62, -41.64 and-17.87, -40.80, all unimodal, indicating the presence of two P atoms of different chemical environment, PPh on 2 thiophene rings, in ligands and complexes 1-32The structure is symmetrical. 2 PPh2The ratio of the integrated area of the peak P to the integrated area of P with 2 thiophene rings attached is 2: 1.
2.2 Crystal Structure
The structure of the complex 1-3 is shown in figure 11, 1 THF (tetrahydrofuran) molecule is used as a solvent in 1 molecule of 2 complexes, 0.5 n-hexane molecule is used as a solvent in 2 molecules of 2 complexes, and no solvent molecule is contained in the crystal structure of the complex 3. The crystal data and the selected bond length and bond angle data are shown in tables 1 and 2. The crystal structure of the complex 1-3 shows that the complex 1-3 is a mononuclear copper four-coordination structure and is in a distorted tetrahedral configuration, 2P-Cu-P bond angles are 85.31-87.73 degrees, and the angle is greatly different from the common tetrahedral bond angle because of the small occlusion angle in the DTTP ligand. As shown in Table 2, the Cu-X bond length in complexes 1-3 is
The bond length increases with increasing van der waals radius of the halogen. In 1-3, intermolecular hydrogen bonding of halogen to H atom on benzene ring in adjacent molecule was observed, wherein distances of I … H, Br … H and Cl … H were 3.051, 2.904 and
due to the solvent THF molecule in complex 1, it can be observed that the distance between the H atom in THF and the H of the methyl group on the thiophene ring is
C-H … pi acting force exists between C-H bond in THF and benzene ring on diphenylphosphine, and the shortest distance between C on benzene ring and H in THF is
The complex 2 contains n-hexane molecules as a solvent, C-H … pi acting force exists between a C-H bond in the n-hexane and a benzene ring on diphenylphosphine, and the shortest distance between C on the benzene ring and H in the n-hexane is
In summary, all these intermolecular interactions combine to form a 1-D ribbon structure along the b-axis, 2 along the a-axis, and 3 a 2D planar structure along the a-and c-axes.
TABLE 1 Crystal data for complexes 1-3
TABLE 2 bond Angle (deg) and bond Length of the Crystal Structure of complexes 1-3
Data of
2.3 Infrared Spectrum
FIG. 12 is a solid infrared spectrum of ligand DTPP and complexes 1-3. At 3054cm-1Is a peak caused by stretching vibration of a C-H bond of a benzene ring or a thiophene ring; at 2919 and 2848cm-1The absorption peak of (2) is a stretching vibration peak of a C-H bond of a methyl group. At 1581cm-1,1477cm-1And 1432cm-1The absorption peaks appearing at the left and right are the vibration peaks of the benzene ring or the thiophene ring framework. At 1178 and 1027cm-1The absorption peaks appearing on the left and right are due to in-plane bending vibration of the C-H bond on the thiophene or benzene ring. At 741cm-1,697cm-1The absorption peaks appearing on the left and right are caused by out-of-plane bending vibration of the C-H bond on the benzene ring in the molecule. From the infrared absorption comparison chart of the ligand and the complex in the figure, it can be seen that the infrared absorption spectrum of the ligand and the complex does not change much, which is consistent with the characteristic that the structure of the complex itself contains the ligand.
2.4 photophysical properties and molecular orbital calculations:
ligand DTTP and complex 1-3 in CH at room temperature2Cl2The absorption spectrum in (2) is shown in FIG. 13. The absorption spectrum of the ligand is 266 (. epsilon.). sup.1.54X 104M-1cm-1)、291nm(ε＝1.27×104M-1cm-1) Has a strong absorption band, which is the characteristic absorption peak of the thienylphosphine compound and the arylphosphine compound. The absorption peak is a mixed transition due to electron transfer of n-pi and pi-pi; the former is the electron transition from a lone pair of electrons on the P atom to the empty anti-bond pi-orbitals on the thiophene ring or benzene ring, and the latter is the transition from the phenyl group or internal electrons on the thiophene ring. The complex 1-3 is 271[ epsilon ═ (1.92-2.08). times.104M-1cm-1]And 324nm [ epsilon ] (1.89-2.06). times.104M-1cm-1]Is strong at the placeA weaker absorption tail band at 375-450 nm. The TDDFT calculation results show that HOMO orbitals in the complexes 1-3 are mainly distributed on benzene rings of diphenylphosphine and phosphorus and dimethylthiophene of phenylphosphine (FIGS. 14-16, tables 3-5), and LUMO orbitals are mainly distributed on benzene rings of diphenylphosphine and benzene rings of phenylphosphine, which indicates that the lowest excited state of the complexes 1-3 is a charge transition centered on the ligand.
Table 3.Computed excitation states for complex 1in CH2Cl2.
Table 4.Computed excitation states for complex 2in CH2Cl2.
Table 5.Computed excitation states for complex 3in CH2Cl2.
FIG. 20 is an emission spectrum of complexes 1 to 3 in the state of solid powder at 293K and 77K, and Table 6 is data of maximum emission wavelength, lifetime of 293K and 77K, quantum efficiency, and structure obtained by X-ray analysis calculated by TDDFT. The complex 1-3 emits strong yellow green light, the maximum emission wavelength is 502-528 nm, and the room-temperature solid absolute internal quantum efficiency phi isPLWide emission spectrum, no structural features, indicating that the emission excited state has charge transfer characteristics. 1-3 has an emission maximum wavelength order of 1<2<3, in accordance with the sequence of the halogen ligand field strengths (I)-<Br-<Cl-) Probably because the triplet excited state of 1-3 is to some extent subjected to X-→π*(dpmt) charge transfer transition effects. Color of complexes 1-3 based on fluorescence spectra of 293KThe degree coordinate values are (0.2838,0.4647), (0.3032,0.5383) and (0.3184,0.5480), respectively (fig. 21). Mononuclear copper (I) iodide complex (lambda) with tridentate phosphine ligand bis (2- (1-diphenylphosphinophenyl) phenylphosphine (TTPP) with similar structureem521nm), the maximum emission wavelength of complex 1 is blue-shifted by 19 nm. Substitution of benzene with an electron-rich dimethylthiophene resulted in a blue shift of complex 1, as expected, due to the increase in LUMO energy level. Radiative decay Rate (K) of complexes 1-3 at 293Kr) Are respectively 1.09X 104，5.2×103And 5.4X 103s-1 Complex 1 has a higher k than 2 and 3rThis is attributable to the spin-orbit coupling effect resulting from the increase in the effect of the heavy atom in the complex 1.
The radiation attenuation lifetimes of complexes 1,2 and 3 at 293K were 19.2, 63.0 and 65.3 μ s, respectively, and those of complexes 1,2 and 3 at 77K were 62.2,850 and 1226 μ s, respectively, with room temperature lifetimes shorter than the low temperature 77K lifetime (shortest 2 orders of magnitude), indicating that complexes 1-3 have TADF phenomenon. The resulting Δ E (S) was calculated based on the difference between the emission peaks of complexes 2 and 3 at room temperature and 77K1-T1) Values of 0.1036 and 0.0394eV,. DELTA.E (S)1-T1) The value is small, favoring TADF. Table 3 shows the singlet and triplet energy levels and Δ E (S) of complexes 1-3 calculated and analyzed using the Natural Bond Orbital (NBO)1-T1) Energy level difference. S of Complex 1-31And T1The energy level differences are 0.2178, 0.2554 and 0.2825eV, and further evidence is provided for proving the TADF effect of the complexes 1-3.
FIG. 22 is a calculated front line molecular orbital diagram, where the HOMO orbital is predominantly distributed on the phenyl ring of diphenylphosphine and the phosphorous and dimethylthiophene of phenylphosphine and the LUMO orbital is predominantly distributed on the phenyl ring of diphenylphosphine and the phenyl ring of phenylphosphine in complexes 1-3, indicating that luminescence is predominantly derived from ligand-centered charge transitions.
TABLE 6 photophysical data of complexes 1-3 in the solid state.
2.5 thermal Properties
The good thermal stability of the complexes is important for application in OLEDs. The decomposition temperature of the complex 1-3 in a nitrogen atmosphere is 385-399 ℃ (figure 23) determined by thermogravimetric analysis (TGA), the complex has good thermal stability, one-step weight loss is shown between 437-449 ℃, and about 80-88% of weight loss can be attributed to loss of DTTP ligand. These data indicate that these complexes can be used to assemble OLEDs using vacuum evaporation and solution methods.
2.6 electroluminescent Properties
The structure of the device assembled by the solution method is ITO/PEDOT, PSS (40 nm)/complex 3(25nm)/TPBi (30nm)/LiF (1nm)/Al (100nm), ITO (indium tin oxide) is used as an anode, PEDOT, PSS (poly 3, 4-vinyl dioxythiophene) and polystyrene sulfonic acid) are used as hole injection layers, the complex 3 with the highest quantum efficiency is selected as a light-emitting layer, and TPBi [1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene]Is an electron transport layer, LiF is an electron injection layer, and Al is a cathode. The results were: the device exhibited yellow light at 580nm, a maximum emission wavelength of 580nm, and a CIE (x, y) of (0.4751, 0.4967). The maximum External Quantum Efficiency (EQE) of the device is 2.18%, and the maximum brightness is 566.8cd/m2. The respective performances are shown in fig. 24.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A mononuclear four-coordination cuprous halide complex of tridentate phosphine ligand based on a dimethylthiophene skeleton is characterized by having the following structural general formula:
wherein X is I, Br or Cl.
2. The synthesis method of the mononuclear four-coordination cuprous halide complex based on tridentate phosphine ligand of the dimethylthiophene skeleton, which is characterized by comprising the following steps:
wherein X is I, Br or Cl.
3. Use of the mononuclear tetracoordinated cuprous halide complex of tridentate phosphine ligand based on dimethylthiophene skeleton according to claim 1, characterized in that: as a fluorescent material.
4. Use of mononuclear tetradentate cuprous halide complexes of tridentate phosphine ligands based on dimethylthiophene skeleton according to claim 3, characterized in that: as a thermally activated delayed fluorescence material.
5. Use of mononuclear, tetradentate cuprous halide complexes of tridentate phosphine ligands based on dimethylthiophene skeleton according to claim 3 or 4, characterized in that: as a yellow-green fluorescent material.
6. Use of the mononuclear tetracoordinated cuprous halide complex of tridentate phosphine ligand based on dimethylthiophene skeleton according to claim 1, characterized in that: as organic light emitting diode materials.
7. An OLED device comprising at least an organic light-emitting layer, characterized in that: the material of the organic light-emitting layer is selected from any one or a mixture of more of the complexes provided in claim 1.
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