With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray...With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1（No. 2） with a = 11.2694（2）, b = 12.3699（3）, c = 15.0387（3） ？, α = 102.840（2）, β = 105.215（2）, γ = 96.388（2）°, V = 1940.04（7） ^3, Z = 1, Dc = 2.438 g·cm^-3, F（000） = 1324, R = 0.0256 and w R = 0.0555（I 〉 2σ（I））. Compound 1 features a discrete anionic moiety of [Cu6I10]^4- charge-balanced by two metal complexes of [Ni（phen）3]2＋. The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant（crystal violet aqueous solution（CV）, 50 m L, 1.0 × 10^-5 M） could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.展开更多
A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal...A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.展开更多
A binuclear cuprous complex [Cu（μ-I）（NP）]2·CH2Cl2（1, NP = 1-（2-（diphenylphosphino）phenyl）-3,5-dimethylpyrazole） was synthesized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-cry...A binuclear cuprous complex [Cu（μ-I）（NP）]2·CH2Cl2（1, NP = 1-（2-（diphenylphosphino）phenyl）-3,5-dimethylpyrazole） was synthesized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 9.2838（6）, b = 12.2672（7）, c = 12.4033（7） A, α = 114.941（6）, β = 108.707（5）, γ = 91.717（5）°, V = 1190.51（12） A3, Z = 1, Mr = 1178.58, Dc = 1.644 g/cm3, F（000） = 582, μ = 13.232 mm-1, GOOF = 1.016, the final R = 0.0384 and wR = 0.1015 for 4145 observed reflections with I 〉 2σ（I）. The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry. In the solid state, the complex exhibits blue photoluminescence with a peak maximum of 468 nm, a decay time of 9 μs, and a photoluminescence quantum yield of 16.8% at room temperature, respectively. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of experimental and DFT calculations suggest that the excited states in the solid state are of（M＋X＋L）LCT character.展开更多
A dinuclear cuprous complex[(mapypz)Cu(μ-I)2 Cu(mapypz)](1,mapypz=9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)-pyridin-3-yl)-9,10-dihydroacridine)was synthesized from the reaction of equivalent CuⅠand mapypz at roo...A dinuclear cuprous complex[(mapypz)Cu(μ-I)2 Cu(mapypz)](1,mapypz=9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)-pyridin-3-yl)-9,10-dihydroacridine)was synthesized from the reaction of equivalent CuⅠand mapypz at room temperature.The compound crystallizes in monoclinic space group P21/c with a=13.8300(4),b=9.5365(2),c=19.0833(5)?,β=103.017(3)o,V=2452.23(11)?3,Z=2,Mr=1237.92,Dc=1.677 g/cm3,F(000)=1232,μ=11.334 mm^–1,GOOF=1.001,the final R=0.0330,and wR=0.0741 for 4627 observed reflections withⅠ>2σ(Ⅰ).The Cu(I)atoms in the complex are four-coordinated with a distorted tetrahedral coordination geometry.The copper centers in the molecular structure are bridged by two iodide anions and each Cu(I)is chelated further terminally by a diimine ligand.The[Cu(μ-I)2 Cu]core is planar.Ⅰn the solid state,the complex exhibits orange photoluminescence with emission peakλmax=568 nm,lifetimeτ=16μs and quantum yieldф=0.22 at room temperature.The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature.The results of experimental and DFT calculations suggest that the emission in the solid state originates from the 1,3 MLCT excited states.展开更多
A new tetranuclear cuprous halide complex,(CuBr)_(4)(PN)_(2)(PN=2-(diphenylphosphaneyl)-6-methoxypyridine),was synthesized and fully characterized.In solid state,this complex exhibits efficient blue emission with a ph...A new tetranuclear cuprous halide complex,(CuBr)_(4)(PN)_(2)(PN=2-(diphenylphosphaneyl)-6-methoxypyridine),was synthesized and fully characterized.In solid state,this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3%and a decay time of 19μs at room temperature.The theoretical calculations,combined with the temperature dependence of spectroscopic properties and emission decay behaviors,indicate that the emission in the solid state originates from the ^(1,3)(MLCT+XLCT)excited states,which are in thermal equilibrium with a small energy gap of about 0.1 eV.展开更多
基金Supported by the NNSFC(No.21373223)Chunmiao project of Haixi Institute of Chinese Academy of Sciences(CMZX-2014-001)
文摘With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1（No. 2） with a = 11.2694（2）, b = 12.3699（3）, c = 15.0387（3） ？, α = 102.840（2）, β = 105.215（2）, γ = 96.388（2）°, V = 1940.04（7） ^3, Z = 1, Dc = 2.438 g·cm^-3, F（000） = 1324, R = 0.0256 and w R = 0.0555（I 〉 2σ（I））. Compound 1 features a discrete anionic moiety of [Cu6I10]^4- charge-balanced by two metal complexes of [Ni（phen）3]2＋. The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant（crystal violet aqueous solution（CV）, 50 m L, 1.0 × 10^-5 M） could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.
基金supported by the National Natural Science Foundation of China(21521061,51672271,21671190)the Natural Science Foundation of Fujian Province(2006L2005)
文摘A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.
基金supported by the National Natural Science Foundation of China(51672271,21521061,21671190,2006L2005,XDB20000000)
文摘A binuclear cuprous complex [Cu（μ-I）（NP）]2·CH2Cl2（1, NP = 1-（2-（diphenylphosphino）phenyl）-3,5-dimethylpyrazole） was synthesized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 9.2838（6）, b = 12.2672（7）, c = 12.4033（7） A, α = 114.941（6）, β = 108.707（5）, γ = 91.717（5）°, V = 1190.51（12） A3, Z = 1, Mr = 1178.58, Dc = 1.644 g/cm3, F（000） = 582, μ = 13.232 mm-1, GOOF = 1.016, the final R = 0.0384 and wR = 0.1015 for 4145 observed reflections with I 〉 2σ（I）. The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry. In the solid state, the complex exhibits blue photoluminescence with a peak maximum of 468 nm, a decay time of 9 μs, and a photoluminescence quantum yield of 16.8% at room temperature, respectively. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of experimental and DFT calculations suggest that the excited states in the solid state are of（M＋X＋L）LCT character.
文摘A dinuclear cuprous complex[(mapypz)Cu(μ-I)2 Cu(mapypz)](1,mapypz=9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)-pyridin-3-yl)-9,10-dihydroacridine)was synthesized from the reaction of equivalent CuⅠand mapypz at room temperature.The compound crystallizes in monoclinic space group P21/c with a=13.8300(4),b=9.5365(2),c=19.0833(5)?,β=103.017(3)o,V=2452.23(11)?3,Z=2,Mr=1237.92,Dc=1.677 g/cm3,F(000)=1232,μ=11.334 mm^–1,GOOF=1.001,the final R=0.0330,and wR=0.0741 for 4627 observed reflections withⅠ>2σ(Ⅰ).The Cu(I)atoms in the complex are four-coordinated with a distorted tetrahedral coordination geometry.The copper centers in the molecular structure are bridged by two iodide anions and each Cu(I)is chelated further terminally by a diimine ligand.The[Cu(μ-I)2 Cu]core is planar.Ⅰn the solid state,the complex exhibits orange photoluminescence with emission peakλmax=568 nm,lifetimeτ=16μs and quantum yieldф=0.22 at room temperature.The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature.The results of experimental and DFT calculations suggest that the emission in the solid state originates from the 1,3 MLCT excited states.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)the Key Research Program of Frontier Science,CAS(QYZDJ-SSW-SLH033)+3 种基金the National Natural Science Foundation of China(52073286,21805281,21875252)the Natural Science Foundation of Fujian Province(2006L2005,2019J01125)the Youth Innovation Foundation of Xiamen City(3502Z20206082)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR132)。
文摘A new tetranuclear cuprous halide complex,(CuBr)_(4)(PN)_(2)(PN=2-(diphenylphosphaneyl)-6-methoxypyridine),was synthesized and fully characterized.In solid state,this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3%and a decay time of 19μs at room temperature.The theoretical calculations,combined with the temperature dependence of spectroscopic properties and emission decay behaviors,indicate that the emission in the solid state originates from the ^(1,3)(MLCT+XLCT)excited states,which are in thermal equilibrium with a small energy gap of about 0.1 eV.
