CN102746843B - Novel mononuclear copper (I) complex blue light material and preparation method thereof - Google Patents
Novel mononuclear copper (I) complex blue light material and preparation method thereof Download PDFInfo
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- CN102746843B CN102746843B CN 201210256949 CN201210256949A CN102746843B CN 102746843 B CN102746843 B CN 102746843B CN 201210256949 CN201210256949 CN 201210256949 CN 201210256949 A CN201210256949 A CN 201210256949A CN 102746843 B CN102746843 B CN 102746843B
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Abstract
The invention relates to a new luminescent material, in particular to a novel mononuclear copper (I) complex blue light material and a preparation method thereof. The novel mononuclear copper (I) complex blue light material is perchlorate 5-tertiary butyl-3-[2-pyridyl]-1, 2, 4-triazole-bis [triphenylphosphine] copper [I] complex, the molecular formula is C47H44ClCuN4O4P2, and the molecular weight is 889.82. The mononuclear copper (I) complex blue light material provided by the invention is mainly used for luminescent materials in daily lighting, luminescent display and optical sensors. Photoluminescence property test results show that the copper (I) complex has good photoluminescence property in the solid state, strong pure blue light emission is represented, and the maximum value is located at 455 nm.
Description
Technical field
The present invention relates to luminous novel material synthetic technology, particularly relate to a kind of novel monokaryon copper (I) title complex blue light material and preparation method thereof.
Background technology
Transition metal luminescent ligand compound, the impact owing to being subject to heavy atoms effect and strong spin-orbit coupling can utilize singlet state and triplet state at all interior energy, and luminous efficiency can significantly improve.At present, the central atom of transition metal luminescent ligand compound mainly concentrated on for the 5th, six cycles, particularly group VIII transition metal, and ruthenium, osmium, iridium and platinum have occupied the central position of present research.But because transition metal (except a few metal of first and second subgroup) content in the earth's crust in the 5th, six cycles is rare, the exploitation difficulty, therefore the use cost of this class precious metal luminescent ligand compound is higher, and may bring the nervous problem in starting material source after large-scale application.In addition, this class heavy metal complex is usually all toxic, metal complexess such as ruthenium, osmium, rhenium especially, thereby the large-scale application of this class material also can be brought environmental pollution and to producing and the user brings direct injury.High use cost and make their large-scale application be extremely restricted to deficiencies such as environment are unfriendly, so scientists is expected can look for other alternative metallic element outside the 5th, six cycle transition metallic elements.
Compared to the precious metal in the 5th, six cycles, the metallic copper aboundresources in the period 4, cheap and easy to get, and also environmentally friendly.In addition, copper (I) title complex is the title complex that has the visible phosphorescent emissions of room temperature in the period 4 transition metal complex, and luminous peak position changes can change near infrared from ultraviolet, has covered whole visible region.The plurality of advantages such as luminescent properties is good, cheap and environmentally friendly make copper (I) luminescent ligand compound show good application prospect in fields such as luminescent device, optical pickocff, nonlinear optical material, dye sensitization solar batterys.
Copper (I) the luminescent ligand compound of reporting in document at present mainly contains [Cu (N^N)
2]
+[Cu (N^N) (P^P)]
+Two large classes, however the latter has better luminescent properties and stability usually.Application contains the pyridines chelating ligand of 1,2,4-triazole, and organophosphorus ligand is as assistant ligand, and the synthetic univalent copper complex luminescent material of design 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 novel monokaryon copper (I) title complex blue light material;
Two of purpose of the present invention is to provide a kind of novel monokaryon copper (I) title complex blue light material preparation method.
Technical solution of the present invention: a kind of novel monokaryon copper (I) title complex blue light material, that is: the perchlorate 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole two [triphenylphosphine] closes copper [I] title complex, its molecular formula: C
47H
44ClCuN
4O
4P
2, molecular weight: 889.82,
Molecular structure is:
Prepare one of method of described a kind of novel monokaryon copper (I) title complex blue light material:
Under nitrogen protection, mol ratio is the [Cu (MeCN) of 1: 1.05
2(PPh
3)
2] (ClO
4) and the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand [being called for short bptzH] stirring at normal temperature in dichloromethane solvent was reacted 4-6 hour, afterwards on Rotary Evaporators with the solvent evaporate to dryness, be that the methylene dichloride-sherwood oil mixed solvent of 1: 6 carries out recrystallization with volume ratio, the crystalline products that filtration and recrystallization obtains, and with ether washing 3-4 time, obtain solid-state faint yellow product after vacuum-drying.
Prepare described a kind of novel monokaryon copper (I) title complex blue light material method two:
Under nitrogen atmosphere, mol ratio is the [Cu (MeCN) of 1: 2.5: 1.05
4] (ClO
4), triphenylphosphine [is called for short PPh
3], the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand stirring at normal temperature in dichloromethane solvent was reacted 4-6 hour, afterwards on Rotary Evaporators with the solvent evaporate to dryness, be that the methylene dichloride-sherwood oil mixed solvent of 1: 6 carries out recrystallization with volume ratio, the crystalline products that filtration and recrystallization obtains, and with ether washing 3-4 time, obtain solid-state faint yellow product after vacuum-drying.
Prepare described a kind of novel monokaryon copper (I) title complex blue light material method three:
Under nitrogen atmosphere, mol ratio is perchlorate hexahydrate's copper [Cu (ClO of 1: 3.5: 1.05
4)
26H
2O], triphenylphosphine, the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand stirring at normal temperature in dichloromethane solvent was reacted 4-6 hour, afterwards on Rotary Evaporators with the solvent evaporate to dryness, be that the methylene dichloride-sherwood oil mixed solvent of 1: 6 carries out recrystallization with volume ratio, the crystalline products that filtration and recrystallization obtains, and with ether washing 3-4 time, obtain solid-state faint yellow product after vacuum-drying.
Prepare described a kind of novel monokaryon copper (I) title complex blue light material method four:
Under nitrogen atmosphere, mol ratio is 1: 5-10: 4.2: 2.1 perchlorate hexahydrate's copper [Cu (ClO
4)
26H
2O], excessive copper powder, triphenylphosphine, the 5-tertiary butyl-3-[2-pyridyl]-1,2, the 4-Triazole ligand is stirring at room reaction 4-6 hour in the acetonitrile of 3: 5 and dichloromethane solvent in volume ratio, after filtering on Rotary Evaporators with the solvent evaporate to dryness, be that 1: 6 methylene dichloride-sherwood oil mixed solvent carries out recrystallization with volume ratio, the crystalline products that filtration and recrystallization obtains, and with ether washing 3-4 time, obtain solid-state faint yellow product after vacuum-drying.
Described solid-state faint yellow product is the perchlorate 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole two [triphenylphosphine] closes copper [I] title complex.
The reaction mechanism that the present invention adopts is as follows:
The physical parameter of gained monokaryon copper [I] title complex is as follows:
Molecular formula: C
47H
44ClCuN
4O
4P
2
Molecular weight: 889.82,
Chinese: the perchlorate 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole two [triphenylphosphine] closes copper [I] title complex,
English name: [Cu[I] [5-tert-butyl-3-(pyridine-2-yl)-1H-1,2,4-triazole] [triphenylphosphine]
2] [ClO
4], be abbreviated as: [Cu[I] [bptzH] [PPh
3]
2] [ClO
4].
Monokaryon copper of the present invention (I) title complex blue light material is mainly used in the luminescent material in normal lighting, luminescence display and optical sensor device.
In the present invention, monokaryon copper [I] title complex is introduced the major advantage of tertiary butyl group: the introducing that the large volume tertiary butyl is rolled into a ball causes the space multistory steric hindrance to the coordination triphenylphosphine, can effectively reduce the structure Relaxation of product, thereby improves the luminous quantum efficiency of product; Give by force the introducing of electronic property tertiary butyl group, can further promote the energy level of title complex HOMO highest occupied molecular orbital (HOMO), dwindle HOMO and LUMO level spacing, make product emission wavelength generation blue shift, move to blue light region; The introducing of tertiary butyl group also can increase solvability and the film-forming properties of product.
The photoluminescence performance test result shows, this copper [I] title complex has good photoluminescence performance when solid-state, show a strong ethereal blue light emission, and its maximum value is positioned at 455nm.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Wherein, perchlorate hexahydrate's copper, copper powder, triphenylphosphine: available from Shanghai reagent company of traditional Chinese medicines group,
The 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole: according to document " G.Kuzuya, M.Matsui, K.Shibata, J.Chem.Res.Miniprint 1999,1301 for K.Funabiki, N.Noma " described method self-control.
Embodiment 1
Under nitrogen atmosphere, [Cu (MeCN)
2(PPh
3)
2] (ClO
4) (385mg, 0.50mmol) and the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand (106mg, 0.52mmol) (both mol ratios are 1: 1.05) stirring at normal temperature reaction 4 hours in the 50mL dichloromethane solvent, afterwards on Rotary Evaporators with the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (15mL)-sherwood oil (90mL) mixed solvent [volume ratio is 1: 6].The crystalline products that filtration and recrystallization obtains with 60mL ether washing 3-4 time, can obtain a faint yellow solid product (378mg, 0.42mmol) after vacuum-drying, productive rate is about 84%.
Proton nmr spectra (400MHz, DMSO-d
6, ppm) δ: 14.72 (s, 1H), 8.23 (d, 1H, J=8.0Hz), 8.04 (t, 1H, J=7.6Hz), 7.91 (s, 1H), 7.49-7.43 (m, 6H), (7.42-7.33 m, 13H), 7.15-7.10 (m, 12H), 1.16 (s, 9H)
Nucleus magnetic resonance phosphorus spectrum (202.3MHz, DMSO-d
6, ppm) δ :-0.19 (s, PPh
3)
Ultimate analysis calculated value (C
47H
44ClCuN
4O
4P
2) be (%): C63.44, H4.98, N6.30; Measured value: C63.25, H5.12, N6.43.
X-ray single crystal diffraction: crystal belongs to oblique system, the C2/c spacer, and unit cell parameters: a=32.625 (4), b=15.5875 (19),
β=124.976 (2) °,
Mr=889.79, Z=8, Dc=1.325g/cm
3, μ=0.669mm
-1.
Embodiment 2
Under nitrogen atmosphere, [Cu (MeCN)
4] (ClO
4) (163mg, 0.50mmol) and triphenylphosphine (328mg, 1.25mmol) stirring reaction can obtain a water white transparency clear liquid in 1 hour in the 50mL dichloromethane solvent, rear past its adds the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand (107mg, 0.53mmol) [three's mol ratio is 1: 2.5: 1.05], continued stirring reaction 3 hours, afterwards on Rotary Evaporators with the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (15mL)-sherwood oil (90mL) mixed solvent [volume ratio is 1: 6].The crystalline products that filtration and recrystallization obtains with 50mL ether washing 3-4 time, can obtain a faint yellow solid product (338mg, 0.38mmol) after vacuum-drying, productive rate is about 76%; The experimental data of proton nmr spectra, phosphorus spectrum and ultimate analysis is with embodiment 1.
Embodiment 3
Under nitrogen atmosphere, perchlorate hexahydrate's copper [Cu (ClO
4)
26H
2O] (185mg, 0.50mmol) and triphenylphosphine (459mg, 1.75mmol) stirring reaction can obtain a clear, colorless clear liquid in 1.5 hours in the 40mL dichloromethane solution, rear past its adds the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand (106mg, 0.52mmol) [three's mol ratio is 1: 3.5: 1.05], continued stirring reaction 4.5 hours, afterwards on Rotary Evaporators with the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (15mL)-sherwood oil (90mL) mixed solvent [volume ratio is 1: 6].The crystalline products that filtration and recrystallization obtains with 55mL ether washing 3-4 time, obtains a faint yellow solid product (356mg, 0.40mmol) after vacuum-drying, productive rate is about 80%; The experimental data of proton nmr spectra, phosphorus spectrum and ultimate analysis is with embodiment 1.
Embodiment 4
Under nitrogen atmosphere, perchlorate hexahydrate's copper [Cu (ClO
4)
26H
2O] (186mg, 0.50mmol) and excessive copper powder (318mg, 5.00mmol) stirring reaction 30 minutes in the 15mL acetonitrile solvent, again successively successively toward its triphenylphosphine (551mg, 2.10mmol), the 5-tertiary butyl-3-[2-pyridyl]-1,2,4-Triazole ligand (212.4mg, 1.05mmol) [four mol ratios are 1: 5-10: 4.2: 2.1] and methylene dichloride 25mL, continued stirring reaction 4.5 hours under normal temperature, after filtering on Rotary Evaporators with the solvent evaporate to dryness, carry out recrystallization with methylene dichloride (15mL)-sherwood oil (90mL) mixed solvent [volume ratio is 1: 6].The crystalline products that filtration and recrystallization obtains with 60mL ether washing 3-4 time, can obtain a faint yellow solid product (730mg, 0.82mmol) after vacuum-drying, productive rate is about 82%; The experimental data of proton nmr spectra, phosphorus spectrum and ultimate analysis is with embodiment 1.
Solid-state faint yellow product described in embodiment is the perchlorate 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole two [triphenylphosphine] closes copper [I] title complex.
Claims (1)
1. novel monokaryon copper (I) title complex blue light material, that is: the perchlorate 5-tertiary butyl-3-[2-pyridyl]-1,2,4-triazole two [triphenylphosphine] closes copper [I] title complex, its molecular formula: C
47H
44ClCuN
4O
4P
2, molecular weight: 889.82,
Molecular structure is:
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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 |
| CN104844629B (en) * | 2015-04-14 | 2017-08-11 | 苏州大学 | A kind of monokaryon copper [I] complex material of blue or/and green emission |
| 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 |
| CN105153225A (en) * | 2015-10-16 | 2015-12-16 | 江西理工大学 | Methylpyridyl triazole copper [I] neutral complex luminescent materials and preparation method thereof |
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