CN109320530B - High-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and synthetic method and application thereof - Google Patents
High-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and synthetic method and application thereof Download PDFInfo
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003446 ligand Substances 0.000 title claims abstract description 61
- 150000004820 halides Chemical class 0.000 title claims abstract description 36
- UJQHSJQQSJRGLA-UHFFFAOYSA-N P.P.CC1=C(SC=C1)C Chemical compound P.P.CC1=C(SC=C1)C UJQHSJQQSJRGLA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- NTWUXYINRXEGQZ-UHFFFAOYSA-N (4-diphenylphosphanyl-2,5-dimethylthiophen-3-yl)-diphenylphosphane Chemical group C1(=CC=CC=C1)P(C1=C(SC(=C1P(C1=CC=CC=C1)C1=CC=CC=C1)C)C)C1=CC=CC=C1 NTWUXYINRXEGQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NWYUIYYDNDZXBK-UHFFFAOYSA-N 3,4-dibromo-2,5-dimethylthiophene Chemical compound CC=1SC(C)=C(Br)C=1Br NWYUIYYDNDZXBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- BHMGWSQPCUJGMR-UHFFFAOYSA-N [Li].[Li].CC=1SC(=CC1)C Chemical compound [Li].[Li].CC=1SC(=CC1)C BHMGWSQPCUJGMR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000007787 solid Substances 0.000 abstract description 11
- 238000001308 synthesis method Methods 0.000 abstract description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 230000005281 excited state Effects 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- BZYUMXXOAYSFOW-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical compound CC=1C=CSC=1C BZYUMXXOAYSFOW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PWNHMYPRQAUDMJ-UHFFFAOYSA-N (2,3-dimethylphenyl)-phenylphosphane Chemical compound CC1=CC=CC(PC=2C=CC=CC=2)=C1C PWNHMYPRQAUDMJ-UHFFFAOYSA-N 0.000 description 1
- MAYBLAMHJYPCKA-UHFFFAOYSA-N (2-diphenylphosphanyl-4,5-dimethylphenyl)-diphenylphosphane Chemical compound C1(=CC=CC=C1)P(C1=C(C=C(C(=C1)C)C)P(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 MAYBLAMHJYPCKA-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BZDNMSNFLZXRLY-UHFFFAOYSA-N [2-(diphenylphosphanylmethyl)phenyl]methyl-diphenylphosphane Chemical compound C=1C=CC=C(CP(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1CP(C=1C=CC=CC=1)C1=CC=CC=C1 BZDNMSNFLZXRLY-UHFFFAOYSA-N 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
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 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
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 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
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002503 iridium Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- -1 thiophene-substituted benzenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention relates to a high-efficiency blue light cuprous halide complex containing a dimethyl thiophene diphosphine and triphenylphosphine ligand, and a synthesis method and application thereof. The complex is a four-coordination mononuclear cuprous halide complex, and the molecular formula of the complex is as follows: [ CuX (dpmt)) (PPh3)]Wherein: dpmt is 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene, and X is either I, Br or Cl. The target complex has high yield, the synthetic method is simple and easy to operate, expensive instruments and equipment are not needed, and the industrialization is facilitated. In addition, the target complex emits strong blue light at solid room temperature, the maximum emission wavelength is 447-460 nm, the light-emitting life is 219-830 mu s, and the absolute quantum efficiency phi is 0.26-0.45.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a high-efficiency blue-light cuprous halide complex containing diphosphine dimethylthiophene and triphenylphosphine ligands, and a synthesis method and application thereof.
Background
Phosphorescent cuprous complexes, a new class of electroluminescent materials for Organic Light Emitting Diodes (OLEDs), have attracted considerable attention because of their advantages of large abundance and low price compared to the third row of transition metals, such as iridium and platinum. The organic-metallic cuprous complex with small singlet state and triplet state energy level difference can effectively capture triplet state excitons to generate activation delayed fluorescence.
Recently, Osawa et al reported a three-coordinate green cuprous halide complex with 1, 2-di (o-xylylphosphino) benzene with an External Quantum Efficiency (EQE) of more than 20%. This efficiency is comparable to devices assembled with cyclometalated iridium complexes. To date, few reports have been made of cuprous complexes that thermally activate delayed fluorescence with high efficiency blue light, as compared to the numerous reported green cuprous complexes. The exploration of a new high-efficiency cuprous complex with the luminescent wavelength of 400-460 nm is of great significance to full-color display and solid-state illumination.
The inventor subjects group studied earlier and contained dpmb and PPh3In the high-efficiency blue light cuprous complex, the maximum emission wavelength is 464-479 nm. The introduction of electron donating groups can increase the LUMO energy level, resulting in a blue shift of the maximum emission wavelength. Thiophene is an electron-rich heterocyclic ring and can be used as an electron donor material to be applied to a solar cell. In view of the above considerations, we have selected thiophene-substituted benzenes for the construction of rigid bisphosphine ligands, with ligands PPh3Together, it is possible to obtain a high efficiency blue cuprous complex.
Disclosure of Invention
The invention aims to provide a high-efficiency blue-light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and a synthesis method and application thereof. The invention discloses a series of cuprous halide complexes containing a tetradentate mononuclear dimethylthiophene diphosphine and triphenylphosphine ligand, and researches the structures and the photophysical properties of the cuprous halide complexes.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
a high-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand is a four-coordination mononuclear cuprous halide complex, and the molecular formula is as follows: [ CuX (dpmt)) (PPh3)]Wherein: dpmt is 3, 4-di (diphenylphosphino) -2, 5-dimethylthiophene, and X is any one of I, Br or Cl; the mononuclear copper in the complex is respectively connected with 3P and 1 halogen atoms to form a highly distorted tetrahedral configuration, and the molecular structural formula of the complex is shown as the following formula I:
further, the aboveWhen the X is I, the complex is a high-efficiency blue light cuprous iodide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and the structure of the complex also contains 3 solvents CH2Cl2A molecule having the empirical formula: c48H41CuIP3S·3(CH2Cl2) Molecular weight is 1188.00, the complex belongs to a triclinic system, space group is P-1, and unit cell parameters
And Z is 2, and the crystal is colorless.
Further, when X ═ Br in the above technical scheme, the complex is a high-efficiency blue light cuprous bromide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand, and the complex structure also contains 3 solvents CH2Cl2A molecule having the empirical formula: c48H41CuBrP3S·3(CH2Cl2) Molecular weight is 1141.01, the complex belongs to a triclinic system, space group is P-1, and unit cell parameters
And Z is 2, and the crystal is colorless.
Further, when X ═ Cl in the above technical scheme, the complex is a high-efficiency blue light cuprous chloride complex containing a dimethylthiophene diphosphine and a triphenylphosphine ligand, and the experimental formula of the complex is: c48H41CuClP3S, molecular weight is 841.77, the complex belongs to monoclinic system, space group is P2(1)/n, unit cell parameter
And Z is 4, and the crystal is colorless.
The second purpose of the invention is to provide a synthesis method of the high-efficiency blue-light cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand, which comprises the following steps:
firstly, uniformly mixing 2, 5-dimethyl-3, 4-dibromothiophene with n-butyllithium in proportion at the temperature of-78 ℃ in Tetrahydrofuran (THF) under nitrogen atmosphere to synthesize a 2, 5-dimethylthiophene dilithium reagent, then adding diphenyl phosphine chloride, and after the reaction is finished, separating and purifying to obtain a ligand dpmt; then the purified dpmt ligand and cuprous halide (CuX) are put in dichloromethane (CH)2Cl2) Mixing, adding PPh3And (3) stirring the ligand overnight, and finally separating and purifying to obtain the cuprous halide complex containing the dimethyl thiophene diphosphine and triphenylphosphine ligand.
Further, the molar ratio of 2, 5-dimethyl-3, 4-dibromothiophene to n-butyllithium in the above technical scheme is 1: 2.
further, the equivalent ratio of the dpmt ligand to the CuX in the above technical scheme is 1: 1.
further, the CuX and the PPh in the technical scheme3The equivalent ratio of the ligands is 1: 1.
the synthetic route of the cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand is shown as a formula II:
the third purpose of the invention is to provide the application of the high-efficiency blue light cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand, and the complex can be used as an electroluminescent material to assemble an organic light-emitting diode (OLED).
The invention relates to an electroluminescent material for assembling an OLED, which is a high-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand.
Compared with the prior art, the invention has the following beneficial effects:
(1) the target complex synthesized by the method has high yield which reaches 81-87%, and the synthesis method is simple and easy to operate, does not need expensive instruments and equipment, and is beneficial to industrialization;
(2) the target complex emits strong blue light at solid room temperature, the maximum emission wavelength is 447-460 nm, the luminescence life is 219-830 mu s, the absolute quantum efficiency phi is 0.26-0.45, and luminescence mainly comes from transition of charges from metal to ligand, halogen to ligand and ligand, so that the target complex can be used as an electroluminescent material to assemble an OLED (organic light emitting diode) and has a good application prospect.
Drawings
FIG. 1 shows ORTEP diagrams of complexes 1 to 3 synthesized in examples 2 to 4 of the present invention;
FIG. 2 shows the ligands dpmt, PPh of the invention3And complex 1-3 at room temperature in CH2Cl2The absorption spectrum contrast graph in (1);
in FIG. 3, (a), (b) and (c) are S of complexes 1 to 3 synthesized in examples 2 to 4 of the present invention, respectively0Electron cloud profiles of configurations, HOMO and LUMO;
in FIG. 4, (a) and (b) are respectively solid state emission spectra of complexes 1 to 3 synthesized in examples 2 to 4 of the present invention at 293K and 77K;
FIG. 5 is a CIE diagram of complexes 1-3 synthesized in examples 2-4 of the present invention;
FIG. 6 is a TGA graph of complexes 1-3 synthesized in examples 2-4 of the present invention.
Detailed Description
The following is a detailed description of embodiments of the invention. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
All reagents used in the following examples of the present invention 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 reported literature. The infrared spectrum was obtained by a Nicolet iS10FTIR Fourier transform infrared spectrometer (KBr pellet),1H,13c and31p NMR spectra were obtained using a Varian 600MHz 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.
Unless otherwise specified, 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene (dpmt) used in examples 2 to 4 described below was synthesized by the method of example 1.
Example 1
The 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene (dpmt) of this example was prepared as follows, including the following steps:
3, 4-dibromo-2, 5-dimethylthiophene (6.0g,22.22mmol) was dissolved in 70mL of THF, cooled to-78 deg.C, and 18.8mL (47.00mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise, stirring was continued for 0.5h, a solution of diphenylphosphine chloride (10.37g,47.00mmol) in THF (35mL) was added, and stirring was continued for 0.5 h; the solution was then 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: dichloromethane ═ 1:4) to give a pure white product (7.45g, 69.8%). The test results of the obtained product are respectively as follows:
1H NMR(600MHz,d6-DMSO):7.33-7.27(m,12H),7.20-7.17(m,8H),1.81(s,6H).13C NMR(150MHz,CDCl3),＝144.33,144.30,136.20,132.39,132.36,132.31,132.29,132.24,132.21,128.12,127.66,15.68.31P NMR(240MHz,CDCl3),＝-21.45.MS(MALDI-TOF):m/z calcd for C30H26P2S 481.1264,found 481.1231.Anal.Calcd for C30H26P2S:C,74.98；H,5.45.Found:C,74.93；H,5.42.
example 2
The high-efficiency blue light cuprous iodide complex (complex 1) containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand is prepared by the following method, and comprises the following steps:
cuprous iodide (0.159g,0.83mmol) was added to 20mL CH dissolved with dpmt (0.402g,0.83mmol)2Cl2To the solution, the mixture was stirred at room temperature for 5 hours, the reaction mixture was filtered, and the solvent was removed under reduced pressure to give a pale yellow powder. The powder was dissolved in 20mL of dichloromethane and PPh was added3(0.218g,0.83mmol) and the mixture stirred overnight to form a colorless liquid which was slowly evaporated at room temperature to precipitate colorless microcrystals which were filtered and then concentrated in CH2Cl2Recrystallization from Celite gave 0.644g of colorless crystals, i.e.Compound 1, as 82.7%. The test results of the obtained product are respectively as follows:
1H NMR(600MHz,CDCl3):7.80-7.65(m,3H),7.40-7.26(m,5H),7.23(t,J＝9Hz,4H),7.15-7.00(m,16H),6.99-6.80(m,7H),1.79(s,6H).31P NMR(240MHz,CDCl3):-0.82(s),-21.02(s).Anal.Calcd for C48H41CuIP3S:C,61.77；H,4.43.Found:C,61.73；H,4.45.MS(MALDI-TOF):m/z calcd for[2M-2Cl-2PPh3-Cu-H]+,1022.1673,found:1022.8572.
example 3
The high-efficiency blue light cuprous bromide complex (complex 2) containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand is prepared by the following method, and comprises the following steps:
the synthesis method of complex 2 in this example is substantially the same as that of complex 1, except that: this example used cuprous bromide (0.119g,0.83mmol) instead of cuprous iodide in CH2Cl2/CH3Recrystallization from CN gave 0.641g of complex 2 as colorless crystals in 86.7% yield. The test results of the obtained product are respectively as follows:
1H NMR(600MHz,CDCl3):7.85-7.72(m,3H),7.38-7.27(m,5H),7.21(t,J＝9Hz,4H),7.15-7.00(m,16H),6.95-6.75(m,7H),1.79(s,6H).31P NMR(240MHz,CDCl3):0.18(s),-19.95(s).Anal.Calcd for C48H41CuBrP3S:C,65.05；H,4.66.Found:C,65.09；H,4.63.MS(MALDI-TOF):m/z calcd for[2M-2Br-2PPh3-Cu-H]+,1022.1673,found:1022.8013.
example 4
The high-efficiency blue light cuprous chloride complex (complex 3) containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand is prepared by the following method, and comprises the following steps:
the synthesis method of complex 3 in this example is substantially the same as that of complex 1, except that: this example used cuprous chloride (0.082g,0.83mmol) instead of cuprous iodide and recrystallized to give 0.569g of complex 3 as colorless crystals with a yield of 81.1%. The test results of the obtained product are respectively as follows:
1H NMR(600MHz,CDCl3):7.90-7.70(m,3H),7.45-7.27(m,5H),7.21(t,J＝9Hz,4H),7.15-6.97(m,16H),6.96-6.68(m,7H),1.79(s,6H).31P NMR(240MHz,CDCl3):0.69(s),-18.64(s).Anal.Calcd for C48H41CuClP3S:C,68.48；H,4.91.Found:C,68.51；H,4.93.MS(MALDI-TOF):m/z calcd for[2M-2Cl-2PPh3-Cu-H]+,1022.1673,found:1022.7913.
TABLE 1 Crystal data sheet of complexes 1-3
TABLE 2 comparison table of bond length and bond angle selected by complexes 1-3
FIG. 2 shows the ligands dpmt, PPh3And complex 1-3 at room temperature in CH2Cl2Absorption spectrum of (1). The concentration of the ligand and the complex is 4 x 10-5And M. The ligand dpmt has a maximum absorption peak at 292nm (1.52 multiplied by 10)4M-1cm-1)，PPh3Has a maximum absorption peak at 278nm (═ 8.23X 10)3M-1cm-1) The characteristic absorptions attributed to thiophenophosphine and phenylphosphine compounds, corresponding to n-pi and pi-pi mixed transitions, are similar to the tetracoordinated mononuclear cuprous complexes. The absorption band of the complex 1-3 is 281-286 nm [ ((1.32-1.60) × 10 [)4M-1cm-1]Broad shoulder 312nm and a weak absorption tail 360-400 nm this weak absorption tail may correspond to a copper to ligand, halogen to ligand or intra-ligand charge transition. Electrons of HOMO orbitals in the complexes 1-3 obtained by TDDFT calculation are mainly distributed on copper atoms, halogen atoms and phosphorus atoms, andthe electrons of the LUMO orbital are mainly distributed on the benzene and thiophene rings (fig. 3). Therefore, we can conclude that the lowest excited state of complexes 1-3 is composed of MLCT, XLCT and ligand internal transition, similar to the related tetrahedral complexes.
FIG. 4 shows solid state emission spectra of complexes 1-3 at 293K and 77K, and Table 3 shows data of maximum emission wavelength, lifetime of 293K and 77K, quantum efficiency, and the like. The complex 1-3 emits strong blue light, the maximum emission wavelength is 447-460 nm, and the room-temperature solid absolute internal quantum efficiency phi isPLThe emission spectrum is wide, and the emission excited state has no structural characteristics, so that the emission excited state has charge transfer characteristics. The emission maximum wavelength sequence of the complexes 1-3 is the complex 1<Complex 2<The order of the field strengths of the complexes 3 and the halogen ligands is identical (I)-<Br-<Cl-) Probably because the triplet excited state of the complexes 1 to 3 is affected to some extent by X-→π*(dpmt) charge transfer transition effects. With a mixture containing 1, 2-bis (diphenylphosphino) -4, 5-dimethylbenzene and PPh3Compared with the solid emission of the mononuclear cuprous halide of the ligand, the blue shift of the complex 1 is 32nm, the blue shift of the complex 2 is 8nm, and the blue shift of the complex 3 is 4 nm. Based on the fluorescence spectrum of 293K, the chromaticity coordinate values of complexes 1-3 are (0.1594,0.1221), (0.1573,0.1609) and (0.1672,0.1865), respectively (FIG. 5), and are close to saturated blue light (0.140, 0.080).
At 77K, the maximum emission wavelengths of the complexes 1-3 are 463 nm, 472 nm and 478nm, and compared with the maximum emission wavelength at room temperature, the emission band is red-shifted due to the excited state (T) with lower energy level at low temperature1) Is dominant. The energy level difference delta E (S) of the complexes 1-3 is calculated from the emission peaks 293K and 77K1-T1) 0.0958,0.0862 and 0.1016eV, respectively. In addition, complexes 1-3 under 293K have long radiation attenuation life, which is1 to 2 orders of magnitude shorter than 77K, indicating TADF phenomenon. Computing optimized excited state S using TDDFT1And T1Δ E ofadi(S1-T1) (Table 3), the small energy level difference (0.0646-0.1980 eV) proves that the complexes 1-3 have TADF effect.
TABLE 3 comparison table of photo-physical data of complexes 1-3 in solid state
aEmission peak wavelength.
bEmission lifetime, experimental error ± 5%.
cAbsolute quantum efficiency in solid state, experimental error ± 5%.
dAdiabatic excitation energy (S) calculated using TDDFT1And T1Energy level, and S1And T1Energy level difference between
eThe luminescence lifetime has 2 components, and the fast components are listed in parentheses
fThe excited state energy levels were calculated from the 293K and 77K emission peaks.
The good thermal stability of the complexes is important for application in OLEDs. Thermogravimetric analysis (TGA) is adopted to determine that the decomposition temperature of the complexes 1-3 in nitrogen atmosphere is 243-267 ℃ (figure 6), the complexes have good thermal stability, one-step weight loss is shown between 384-404 ℃, the weight loss is about 35-42%, and the complexes can be attributed to halogen loss and PPh loss3A ligand. The weight loss in step 2 is 423-436 ℃, and can be attributed to the decomposition or loss of the dpmt ligand.
In conclusion, the invention synthesizes a series of new diphosphine ligands containing electron-rich aromatic heterocyclic dimethyl thiophene and PPh3A neutral luminescent mononuclear cuprous halide complex of a ligand. The solid complexes emit blue light at room temperature, the maximum emission wavelength is 447-460 nm, and the quantum efficiency is 0.26-0.35. The solid complexes 1 to 3 have a small S1–T1The energy level difference indicates that the luminescence is thermal activation delayed fluorescence at room temperature. Therefore, the neutral mononuclear cuprous halide complex synthesized by the method can be used as a cheap and efficient blue light material to be applied to an electroluminescent material.
Claims (9)
1. A high-efficiency blue light cuprous halide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligands is characterized in that: the fittingThe compound is a four-coordination mononuclear cuprous halide complex, and the molecular formula of the compound is as follows: [ CuX (dpmt)) (PPh3)]Wherein: dpmt is 3, 4-di (diphenylphosphino) -2, 5-dimethylthiophene, and X is any one of I, Br or Cl; the mononuclear copper in the complex is respectively connected with 3P and 1 halogen atoms to form a highly distorted tetrahedral configuration, and the molecular structural formula of the complex is shown as the following formula I:
the high-efficiency blue light cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand is prepared by the following method, and comprises the following steps:
firstly, uniformly mixing 2, 5-dimethyl-3, 4-dibromothiophene and n-butyllithium in proportion at the temperature of-78 ℃ in tetrahydrofuran under nitrogen atmosphere to synthesize a 2, 5-dimethylthiophene dilithium reagent, then adding diphenyl phosphine chloride, and after the reaction is finished, separating and purifying to obtain a ligand dpmt; mixing the purified dpmt ligand with cuprous halide in dichloromethane, and adding PPh3And (3) stirring the ligand overnight, and finally separating and purifying to obtain the cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand.
2. The high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand of claim 1, wherein: when the X is I, the complex is a high-efficiency blue light cuprous iodide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and the structure of the complex also contains 3 solvents CH2Cl2A molecule having the empirical formula: c48H41CuIP3S·3(CH2Cl2) Molecular weight is 1188.00, the complex belongs to a triclinic system, space group is P-1, and unit cell parameters
And Z is 2, and the crystal is colorless.
3. The high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand of claim 1, wherein: when X is Br, the complex is a high-efficiency blue light cuprous bromide complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and the structure of the complex also contains 3 solvents CH2Cl2A molecule having the empirical formula: c48H41CuBrP3S·3(CH2Cl2) Molecular weight is 1141.01, the complex belongs to a triclinic system, space group is P-1, and unit cell parameters
And Z is 2, and the crystal is colorless.
4. The high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand of claim 1, wherein: when X is Cl, the complex is a high-efficiency blue light cuprous chloride complex containing dimethyl thiophene diphosphine and triphenylphosphine ligand, and the experimental formula of the complex is as follows: c48H41CuClP3S, molecular weight is 841.77, the complex belongs to monoclinic system, space group is P2(1)/n, unit cell parameter
And Z is 4, and the crystal is colorless.
5. The high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand according to claim 1, wherein: the molar ratio of the 2, 5-dimethyl-3, 4-dibromothiophene to the n-butyllithium is 1: 2.
6. the high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand according to claim 1, wherein: the equivalent ratio of the dpmt ligand to the cuprous halide is 1: 1.
7. the high-efficiency blue-light cuprous halide complex containing dimethylthiophene diphosphine and triphenylphosphine ligand according to claim 1, wherein: the cuprous halide and the PPh3The equivalent ratio of the ligands is 1: 1.
8. the application of the high-efficiency blue-light cuprous halide complex containing the dimethylthiophene diphosphine and the triphenylphosphine ligand, which is disclosed by claim 1, is characterized in that: the complex can be used as an electroluminescent material to assemble an organic light-emitting diode (OLED).
9. An electroluminescent material for use in assembling an OLED, comprising: the electroluminescent material is the high-efficiency blue-light cuprous halide complex containing the dimethyl thiophene diphosphine and the triphenylphosphine ligand in claim 1.
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