CN103497209B - A kind of double-core copper (I) title complex blue light material and preparation method thereof - Google Patents
A kind of double-core copper (I) title complex blue light material and preparation method thereof Download PDFInfo
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- CN103497209B CN103497209B CN201310475826.9A CN201310475826A CN103497209B CN 103497209 B CN103497209 B CN 103497209B CN 201310475826 A CN201310475826 A CN 201310475826A CN 103497209 B CN103497209 B CN 103497209B
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Abstract
The present invention relates to luminous novel material synthetic technology, particularly relate to a kind of double-core copper (I) title complex blue light material and preparation method thereof.Blue light material of the present invention, that is: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazoles] two [two (diphenylphosphine) amine of N, N-] closes two bronze medals [I] title complex, its molecular formula: C
70h
70cl
2cu
2n
10o
8p
4, molecular weight: 1501.26; Luminescent properties test result shows, it has good solid-state light electroluminescent properties, and show a strong blue emission, maximum value is positioned at 439nm, and luminous quantum efficiency is 34%.
Description
Technical field
The present invention relates to luminous novel material synthetic technology, particularly relate to a kind of double-core copper (I) title complex blue light material and preparation method thereof.
Background technology
Based on the emitting complexes of transition metal, due to heavy atoms effect and the effect of strong Zi Xuan – orbit coupling, can effectively utilize singlet state and triplet energies, luminous efficiency can significantly improve.Current, the central metal atom of emitting complexes mainly concentrates on the 5th, six cycles, particularly group VIII transition metal, and ruthenium, osmium, iridium and platinum occupy the central position of research at present.Due to the 5th, transition metal (except a few metal of first and second subgroup) content in the earth's crust in six cycles is rare, exploitation difficulty, thus the use cost of this metalloid emitting complexes is higher, and may bring the problem of raw material sources anxiety after large-scale application.In addition, this kind of precious metals complex is usually all toxic, especially the metal complexes such as ruthenium, osmium, rhenium, and thus, the large-scale application of this metal complexes luminescent material also can bring environmental pollution and to produce and user brings direct injury.High use cost and their large-scale application is extremely restricted to shortcomings such as environment are unfriendly, therefore chemistry and material supply section scholars expect to look for other alternative transition metal the 5th, outside six cycles.
Compared to the 5th, six cycle metals, the metallic copper of period 4, not only aboundresources, cheap and easy to get, 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 plurality of advantages such as luminescence is excellent, cheap and environmentally friendly make monovalence copper emitting complexes in field performance applications well prospects such as luminescent device, optical sensing, nonlinear optics, dye sensitization solar batterys.
The monovalence copper emitting complexes reported in current document 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.Meanwhile, the monovalence copper metal cluster compound of relatively current extensive research and mononuclear coordination compound, the open report that application nitrogen heterocyclic chelating ligand and organic biphosphine ligand carry out designing and synthesizing monovalence copper double-core emitting complexes is little.
The application 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole chelating ligand, organic pair of phosphine, as assistant ligand, designs and builds monovalence Dinuclear Copper Complex luminescent material and synthetic method thereof, not yet having report at present.
Summary of the invention
An object of the present invention is to provide a kind of double-core copper (I) title complex blue light material;
Two of object of the present invention is to provide a kind of double-core copper (I) title complex blue light material preparation method.
Technical solution of the present invention: a kind of double-core copper (I) title complex blue light material, that is: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazoles] 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:
One of method of a kind of double-core copper (I) title complex blue light material described in preparation:
Under an argon 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 a rotary evaporator by solvent evaporate to dryness, recrystallization is carried out with the dichloromethane-ether mixed solvent that volume ratio is 1:5, the crystalline products that filtration and recrystallization obtains, with washed with diethylether 3-4 time, after vacuum-drying, obtain a rice white solid product---double-core copper (I) title complex blue light material.
The method two of a kind of double-core copper (I) the title complex blue light material described in preparation:
Under an argon atmosphere, mol ratio is perchlorate hexahydrate's copper [Cu (ClO of 1:5-10:2:2
4)
26H
2o], excessive copper powder, N, N-two (diphenylphosphine) amine, the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole is stirring at normal temperature reaction 4-6 hour in acetonitrile-dichloromethane mixed solvent, on a rotary evaporator by solvent evaporate to dryness after filtration, be that 1:5 dichloromethane-ether mixed solvent carries out recrystallization by volume ratio, the crystalline products that filtration and recrystallization obtains, with washed with diethylether 3-4 time, after vacuum-drying, obtain a rice white solid product---double-core copper (I) title complex blue light material.
The reaction mechanism that the present invention adopts is as follows:
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-triazoles] two [two (diphenylphosphine) amine of N, N-] closes 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.
The introducing that in the present invention, double-core copper [I] title complex is rolled into a ball due to the large volume tertiary butyl is to the N of bridging coordination, the space multistory steric hindrance that two (diphenylphosphine) amine ligand of N-causes, effectively can reduce the formation of by product and reduce the structure Relaxation of luminous excited state, thus improving productive rate and the luminous quantum efficiency of product; Strong introducing of giving electronic property tertiary butyl group, significantly can promote the energy level that title complex does not occupy track (LUMO), increases HOMO and LUMO level spacing, makes product emission wavelength that remarkable blue shift occur, move to blue light region; The introducing of tertiary butyl group also can increase solvability and the film-forming properties of product.
Luminescent properties test result shows, double-core copper [I] title complex of the present invention has good solid-state light electroluminescent properties, and show a strong blue emission, maximum value is positioned at 439nm, and luminous quantum efficiency is 34%, and solid state fluorescence emmission spectrum as shown in Figure 1.
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 for illustration of the present invention, but are not used for limiting the scope of the invention.
The 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazoles: according to document record method self-control (K.Funabiki, N.Noma, G.Kuzuya, M.Matsui, K.Shibata, J.Chem.Res.Miniprint 1999,1301).
Embodiment 1
Under an argon atmosphere, equimolar [Cu (MeCN)
4] (ClO
4) (186mg, 0.57mmol) and N, two (diphenylphosphine) amine (219mg of N-, 0.57mmol) in 20mL dichloromethane solvent, stirring at normal temperature reacts 1 hour, the 5-tertiary butyl-3-[2-pyridyl]-1 is added afterwards in this water white transparency reaction solution, 2,4-Triazole ligand (115mg, 0.57mmol), continue stirring reaction 3 hours at normal temperatures, after on a rotary evaporator by 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 washed with diethylether 3-4 time, can obtain a beige solid product after vacuum-drying---and 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 (%): C 56.00, H 4.70, N 9.33; Measured value: C 56.07, H 4.66, N 9.27;
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 as shown in Figure 2.
Embodiment 2
Under an argon atmosphere, perchlorate hexahydrate's copper [Cu (ClO
4)
26H
2o] (167mg, 0.45mmol) with excessive copper powder (229mg, 3.60mmol) stirring reaction 20 minutes in 10mL acetonitrile solvent, after add N, two (diphenylphosphine) amine (348mg of N-, 15mL dichloromethane solution 0.90mmol), continue stirring reaction and after 1 hour, add the 5-tertiary butyl-3-[2-pyridyl]-1 again, 2, 4-Triazole ligand (183mg, 0.90mmol), stirring reaction is continued 3 hours under normal temperature, on a rotary evaporator by solvent evaporate to dryness after filtration, recrystallization is carried out with methylene dichloride (10mL)-ether (50mL) mixed solvent [volume ratio is 1:5].The crystalline products that filtration and recrystallization obtains, with 25mL washed with diethylether 3-4 time, obtains a beige solid product after vacuum-drying---double-core copper (I) title complex blue light material (278mg, 0.185mmol), and productive rate is about 41%; Analysis and characterization experimental data is with embodiment 1.
Claims (3)
1. double-core copper (I) title complex blue light material, that is: perchlorate two [the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazoles] 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 a method for double-core copper (I) title complex blue light material according to claim 1, it is characterized in that: undertaken by following requirement:
Under an argon 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 a rotary evaporator by solvent evaporate to dryness, recrystallization is carried out with the dichloromethane-ether mixed solvent that volume ratio is 1:5, the crystalline products that filtration and recrystallization obtains, with washed with diethylether 3-4 time, after vacuum-drying, obtain a rice white solid product---novel double-core copper (I) title complex blue light material.
3. prepare a method for double-core copper (I) title complex blue light material according to claim 1, it is characterized in that: undertaken by following requirement:
Under an argon atmosphere, mol ratio is perchlorate hexahydrate's copper [Cu (ClO of 1:5-10:2:2
4)
26H
2o], excessive copper powder, N, N-two (diphenylphosphine) amine, the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole is stirring at normal temperature reaction 4-6 hour in acetonitrile-dichloromethane mixed solvent, on a rotary evaporator by solvent evaporate to dryness after filtration, be that 1:5 dichloromethane-ether mixed solvent carries out recrystallization by volume ratio, the crystalline products that filtration and recrystallization obtains, with washed with diethylether 3-4 time, after vacuum-drying, obtain a rice white solid product---novel double-core copper (I) title complex blue light material.
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| 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 |
| CN104877673B (en) * | 2015-06-23 | 2016-11-30 | 江西理工大学 | Pyridine pyrazoles double-core copper [I] complex luminescent material and preparation method |
| CN106085413B (en) * | 2016-07-04 | 2018-08-24 | 湖北工业大学 | A kind of narrow emission hybrid inorganic-organic red light material and preparation method thereof |
| 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 |
| CN107556330B (en) * | 2017-10-31 | 2019-04-12 | 江西理工大学 | A kind of pyridine tetrazole four core copper [I] complex blue light material and preparation method thereof |
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