CN103497209A - Novel binuclear copper (I) complex blue-light material and method for preparing same - Google Patents

Novel binuclear copper (I) complex blue-light material and method for preparing same Download PDF

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CN103497209A
CN103497209A CN201310475826.9A CN201310475826A CN103497209A CN 103497209 A CN103497209 A CN 103497209A CN 201310475826 A CN201310475826 A CN 201310475826A CN 103497209 A CN103497209 A CN 103497209A
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light material
copper
title complex
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陈景林
何丽华
肖义亮
温和瑞
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Jiangxi University of Science and Technology
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Abstract

The invention relates to novel luminescent material synthesis technologies, in particular to a novel binuclear copper (I) complex blue-light material and a method for preparing the same. The molecular formula of the blue-light material, namely a perchlorate di-[5-tertiary butyl-3-(2-pyridyl)-1,2,4-triazole] di-[N,N-dual(diphenyl phosphorous) amine] dimeric copper (I) complex, is C<70>H<70>Cl<2>Cu<2>N<10>O<8>P<4>, and the molecular weight of the blue-light material is 1501.26. The novel binuclear copper (I) complex blue-light material and the method have the advantages that as shown by luminescence test results, the novel binuclear copper (I) complex blue-light material is excellent in solid photo-luminescence performance, a powerful blue-light emission property can be realized, the maximum blue-light emission value is 439nm, and the luminescent quantum efficiency is 34%.

Description

A kind of new double-core copper (I) title complex blue light material and preparation method thereof
Technical field
The present invention relates to luminous novel material synthetic technology, particularly relate to a kind of new double-core copper (I) title complex blue light material and preparation method thereof.
Background technology
Luminescent ligand compound based on transition metal, due to heavy atoms effect and strong Zi Xuan – orbit coupling effect, can effectively utilize singlet state and triplet energies, and luminous efficiency can significantly improve.Current, the central metal atom of luminescent ligand compound mainly concentrated on for the 5th, six cycles, particularly group VIII transition metal, and ruthenium, osmium, iridium and platinum occupy the central position of current research.Transition metal (except a few metal of first and second subgroup) content rareness in the earth's crust due to the 5th, six cycles, the exploitation difficulty, thereby the use cost of this metalloid luminescent ligand compound is higher, and may bring the starting material nervous problem of originating after large-scale application.In addition, this class precious metals complex is usually all toxic, metal complexess such as ruthenium, osmium, rhenium especially, thereby the large-scale application of this metal complexes luminescent material also can be brought environmental pollution and to producing and the user brings direct injury.High use cost and shortcoming makes their large-scale application be extremely restricted to environment is unfriendly etc., so chemistry and material supply section scholars expected to look for other alternative transition metal outside the 5th, six cycles.
Compared to the 5th, six cycle metals, the metallic copper of period 4, aboundresources, cheap and easy to get not only, and also comparatively friendly to environment.In addition, univalent copper complex has the visible phosphorescent emissions of room temperature, and its luminous peak position can change near infrared from ultraviolet, contains whole visible region.The luminous plurality of advantages such as good, cheap and environmentally friendly makes monovalence copper luminescent ligand compound in the fields such as luminescent device, optical sensing, nonlinear optics, dye sensitization solar battery performance applications well prospect.
The monovalence copper luminescent ligand compound of reporting in document at present mainly contains monovalence copper metal cluster compound and monovalence copper mononuclear coordination compound.Monovalence copper mononuclear coordination compound mainly contains [Cu (N^N) 2] +[Cu (N^N) (P^P)] +two large classes, the latter has usually than the former better luminescent properties and stability.Simultaneously, monovalence copper metal cluster compound and the mononuclear coordination compound of relatively current broad research, the application nitrogen heterocyclic chelating ligand and organic biphosphine ligand is designed and the open report of synthetic monovalence copper double-core luminescent ligand compound but seldom.
The application 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole chelating ligand, organic pair of phosphine is as assistant ligand, and design and structure monovalence Dinuclear Copper Complex luminescent material and synthetic method thereof, not yet have report at present.
Summary of the invention
One of purpose of the present invention is to provide a kind of new double-core copper (I) title complex blue light material;
Two of purpose of the present invention is to provide a kind of new double-core copper (I) title complex blue light material preparation method.
Technical solution of the present invention: a kind of new double-core copper (I) title complex blue light material, that is: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole] two [N, two (diphenylphosphine) amine of N-] close two bronze medals [I] title complex, its molecular formula: C 70h 70cl 2cu 2n 10o 8p 4, molecular weight: 1501.26;
Molecular structure is:
Prepare one of method of described a kind of novel double-core copper (I) title complex blue light material:
Under argon gas atmosphere, equimolar [Cu (MeCN) 4] (ClO 4), N, two (diphenylphosphine) amine of N-[being called for short dppa], the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole [being called for short bptzH] is stirring at normal temperature reaction 3-5 hour in dichloromethane solvent, after on Rotary Evaporators by the solvent evaporate to dryness, the methylene dichloride that is 1:5 by volume ratio-ether mixed solvent carries out recrystallization, the crystalline products that filtration and recrystallization obtains, with ether washing 3-4 time, obtain a rice white solid product after vacuum-drying---novel double-core copper (I) title complex blue light material.
Prepare described a kind of novel double-core copper (I) title complex blue light material method two:
Under argon gas atmosphere, perchlorate hexahydrate's copper [Cu (ClO that mol ratio is 1:5-10:2:2 4) 26H 2o], excessive copper powder, N, two (diphenylphosphine) amine of N-, the 5-tertiary butyl-3-[2-pyridyl]-1,2, the 4-triazole is stirring at normal temperature reaction 4-6 hour in acetonitrile-methylene dichloride mixed solvent, after filtration on Rotary Evaporators by the solvent evaporate to dryness, by volume ratio, be that 1:5 methylene dichloride-ether mixed solvent carries out recrystallization, the crystalline products that filtration and recrystallization obtains, with ether washing 3-4 time, obtain a rice white solid product after vacuum-drying---novel double-core copper (I) title complex blue light material.
The reaction mechanism that the present invention adopts is as follows:
Figure BDA0000395022930000022
The physical parameter of gained double-core copper [I] title complex is as follows:
Molecular formula: C 70h 70cl 2cu 2n 10o 8p 4;
Molecular weight: 1501.26;
Chinese: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole] two [N, N-two (diphenylphosphine) amine] close two bronze medals [I] title complex;
English name: [Cu 2[5-tert-butyl-3-(pyridine-2-yl)-1H-1,2,4-triazole] 2[μ-bis (diphenylphosphino) amine] 2] [ClO 4] 2, be abbreviated as: [Cu 2[bptzH] 2[μ-dppa] 2] [ClO 4] 2.
In the present invention, double-core copper [I] title complex is due to the introducing of the large volume tertiary butyl group N to the bridging coordination, the space multistory steric hindrance that two (diphenylphosphine) amine ligands of N-cause, can effectively reduce the formation of by product and reduce the structure Relaxation of luminous excited state, thereby improve productive rate and the luminous quantum efficiency of product; Strong introducing of giving electronic property tertiary butyl group, can significantly promote the energy level that title complex does not occupy track (LUMO), increases HOMO and LUMO level spacing, makes the product emission wavelength that remarkable blue shift occur, and moves to blue light region; The introducing of tertiary butyl group also can increase solvability and the film-forming properties of product.
The luminescent properties test result shows, double-core copper of the present invention [I] title complex has good solid-state light electroluminescent properties, shows a strong blue emission, and maximum value is positioned at 439nm, and luminous quantum efficiency is 34%, and the solid state fluorescence emmission spectrum as shown in Figure 1.
The accompanying drawing explanation
Fig. 1 is blue light material solid state fluorescence emmission spectrum of the present invention.
Fig. 2 is blue light material crystalline structure of the present invention.
Embodiment
Following examples are used for the present invention is described, but are not used for limiting the scope of the invention.
The 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole: according to document record method self-control (K.Funabiki, N.Noma, G.Kuzuya, M.Matsui, K.Shibata, J.Chem.Res.Miniprint1999,1301).
Embodiment 1
Under argon gas atmosphere, equimolar [Cu (MeCN) 4] (ClO 4) (186mg, 0.57mmol) and N, two (diphenylphosphine) amine (219mg of N-, 0.57mmol) in the 20mL dichloromethane solvent, stirring at normal temperature is reacted 1 hour, add the 5-tertiary butyl-3-[2-pyridyl afterwards in this water white transparency reaction solution]-1,2,4-Triazole ligand (115mg, 0.57mmol), continue at normal temperatures stirring reaction 3 hours, after on Rotary Evaporators by the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (8mL)-ether (40mL) mixed solvent [volume ratio is 1:5].The crystalline products that filtration and recrystallization obtains, with 20mL ether washing 3-4 time, can obtain a rice white solid product after vacuum-drying---and novel double-core copper (I) title complex blue light material (201mg, 0.134mmol), productive rate is about 47%.
Electron spray(ES) ion massspectrum (ESI-MS): mass-to-charge ratio (m/z) 650[M – (ClO 4) 2] 2+, 448[Cu 2(dppa) 2] 2+;
Ultimate analysis calculated value (C 70h 70cl 2cu 2n 10o 8p 4) be (%): C56.00, H4.70, N9.33; Measured value: C56.07, H4.66, N9.27;
X-ray single crystal diffraction: crystal belongs to triclinic(crystalline)system, P-1 spacer, unit cell parameters: a=12.8913 (2), b=12.9932 (2), c=14.0137 (2); α=69.5740 (10), β=74.2170 (10), γ=71.0920 (10), V=2047.30 (5) 3, Mr=1647.41, Z=1, Dc=1.336g/cm 3, μ=0.725mm -1, GOF=1.046, crystalline structure is as shown in Figure 2.
Embodiment 2
Under argon gas atmosphere, perchlorate hexahydrate's copper [Cu (ClO 4) 26H 2o] (167mg, 0.45mmol) and excessive copper powder (229mg, 3.60mmol) stirring reaction 20 minutes in the 10mL acetonitrile solvent, after add N, two (diphenylphosphine) amine (348mg of N-, 0.90mmol) the 15mL dichloromethane solution, continue stirring reaction and add again the 5-tertiary butyl-3-[2-pyridyl after 1 hour]-1, 2, 4-Triazole ligand (183mg, 0.90mmol), continue stirring reaction 3 hours under normal temperature, after filtration on Rotary Evaporators by the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (10mL)-ether (50mL) mixed solvent [volume ratio is 1:5].The crystalline products that filtration and recrystallization obtains, with 25mL ether washing 3-4 time, obtains a rice white solid product after vacuum-drying---novel double-core copper (I) title complex blue light material (278mg, 0.185mmol), and productive rate is about 41%; The analysis and characterization experimental data is with embodiment 1.

Claims (3)

1. a new double-core copper (I) title complex blue light material, that is: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole] two [N, two (diphenylphosphine) amine of N-] close two bronze medals [I] title complex, its molecular formula: C 70h 70cl 2cu 2n 10o 8p 4, molecular weight: 1501.26,
Molecular structure is:
2. prepare one of a kind of method of novel double-core copper (I) title complex blue light material, it is characterized in that: undertaken by following requirement:
Under argon gas atmosphere, equimolar [Cu (MeCN) 4] (ClO 4), N, two (diphenylphosphine) amine of N-[being called for short dppa], the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole [being called for short bptzH] is stirring at normal temperature reaction 3-5 hour in dichloromethane solvent, after on Rotary Evaporators by the solvent evaporate to dryness, the methylene dichloride that is 1:5 by volume ratio-ether mixed solvent carries out recrystallization, the crystalline products that filtration and recrystallization obtains, with ether washing 3-4 time, obtain a rice white solid product after vacuum-drying---novel double-core copper (I) title complex blue light material.
3. prepare a kind of novel double-core copper (I) title complex blue light material method two, it is characterized in that: by following requirement, undertaken:
Under argon gas atmosphere, perchlorate hexahydrate's copper [Cu (ClO that mol ratio is 1:5-10:2:2 4) 26H 2o], excessive copper powder, N, two (diphenylphosphine) amine of N-, the 5-tertiary butyl-3-[2-pyridyl]-1,2, the 4-triazole is stirring at normal temperature reaction 4-6 hour in acetonitrile-methylene dichloride mixed solvent, after filtration on Rotary Evaporators by the solvent evaporate to dryness, by volume ratio, be that 1:5 methylene dichloride-ether mixed solvent carries out recrystallization, the crystalline products that filtration and recrystallization obtains, with ether washing 3-4 time, obtain a rice white solid product after vacuum-drying---novel double-core copper (I) title complex blue light material.
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CN104877673A (en) * 2015-06-23 2015-09-02 江西理工大学 Pyridine pyrazole dinuclear copper [1] complex luminescent material and preparation method
CN104974181A (en) * 2014-04-09 2015-10-14 中国科学院理化技术研究所 1,8-naphthyridine binuclear copper (I) complex, preparation method and application
CN106085413A (en) * 2016-07-04 2016-11-09 湖北工业大学 A kind of narrow emission organic inorganic hybridization red light material and preparation method thereof
CN106349258A (en) * 2016-08-25 2017-01-25 江西理工大学 Pyridyl triazole copper [I] complex organic vapor luminescent photochromic material and preparation method
CN107556330A (en) * 2017-10-31 2018-01-09 江西理工大学 A kind of core copper [I] complex blue light material of pyridine tetrazole four and preparation method thereof
CN113278031A (en) * 2021-05-21 2021-08-20 福州大学 Copper-based nanocluster, ionic liquid induced synthesis method and application

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Cited By (11)

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CN104974181A (en) * 2014-04-09 2015-10-14 中国科学院理化技术研究所 1,8-naphthyridine binuclear copper (I) complex, preparation method and application
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CN103951683A (en) * 2014-05-12 2014-07-30 江西理工大学 Novel tri/tetra-coordination dual-core copper [I] coordination compound blue-green materials and preparation method thereof
CN103951683B (en) * 2014-05-12 2015-12-09 江西理工大学 Novel three, four-coordination double-core copper [I] title complex blue green light material and preparation method
CN104877673A (en) * 2015-06-23 2015-09-02 江西理工大学 Pyridine pyrazole dinuclear copper [1] complex luminescent material and preparation method
CN106085413A (en) * 2016-07-04 2016-11-09 湖北工业大学 A kind of narrow emission organic inorganic hybridization red light material and preparation method thereof
CN106349258A (en) * 2016-08-25 2017-01-25 江西理工大学 Pyridyl triazole copper [I] complex organic vapor luminescent photochromic material and preparation method
CN106349258B (en) * 2016-08-25 2017-12-12 江西理工大学 Pyridine triazole copper [I] complex organic vapor light-emitting color-changing materials and preparation method
CN107556330A (en) * 2017-10-31 2018-01-09 江西理工大学 A kind of core copper [I] complex blue light material of pyridine tetrazole four and preparation method thereof
CN113278031A (en) * 2021-05-21 2021-08-20 福州大学 Copper-based nanocluster, ionic liquid induced synthesis method and application
CN113278031B (en) * 2021-05-21 2022-08-09 福州大学 Copper-based nanocluster, ionic liquid induced synthesis method and application

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