In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br...In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.展开更多
The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model wer...The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model were obtained from their electrochemical behavior and electrochemical data. The binding constants( K 2+ ) for Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were 8 51×10 3 L·mol -1 and 3 27×10 3 L·mol -1 , and K +s were 3 09×10 4 L·mol -1 and 5 66×10 3 L·mol -1 respectively. The spectroscopic characteristics of the complexes of Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were studied in detail. Some significant spectroelectrochemical data were obtained. The interaction of DNA with complexes was described.展开更多
The title cluster compound [WS4Cu3Br(bipy)2] has been synthesized by the reaction of (NH4)2, CuBr and 2,2′ bipy in DMF solution. Single crystal X ray diffraction data show that the compound has a nest shaped structur...The title cluster compound [WS4Cu3Br(bipy)2] has been synthesized by the reaction of (NH4)2, CuBr and 2,2′ bipy in DMF solution. Single crystal X ray diffraction data show that the compound has a nest shaped structure. Nonlinear optical properties (NLO) of the cluster were investigated by a Z scan technique with a pulsed laser at 532nm. The cluster exhibits the strong NLO absorption and a self defocusing effect (effective non linear absorption coefficient, α2eff=7.3×10-11mW-1; effective non linear refractive index, n2eff=3.9×10-11esu) when measured in a 6.0×10-4mol·dm-3 DMF solution. CCDC: 200397.展开更多
A new active material for ECL sensor. Ru(phen)2(phen-NICH2Br)(PF6)2 has beendesigned and synthesized. its structure was confirmed by means of IR. MS and 'H NMR. Also.some of its properties such as electrochemstry....A new active material for ECL sensor. Ru(phen)2(phen-NICH2Br)(PF6)2 has beendesigned and synthesized. its structure was confirmed by means of IR. MS and 'H NMR. Also.some of its properties such as electrochemstry. fluorescence and ECL are reported.展开更多
[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthrolin...[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthroline（phen）. The two compounds were characterized by elemental analysis and IR spectrum analysis, respectively. Compound 1 was also characterized by single crystal X-ray diffraction analysis. For compound l, the coordination geometry around the Zn^2＋ is a distorted octahedron, with the bite angles of 76.7（3）°-77.6（4）° for all three phen ligands. Moreover, the thermal behaviors and thermal decomposition kinetics were studied and analyzed. Besides, thermal stability and safety parameters（TsADT, Tb） are 164.7 and 166.4℃ for compound 1, and 149.6 and 150.8℃ for compound 2, respectively.展开更多
基金Supported by the National Natural Science Foundation of China(20936003,21276201)
文摘In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.
文摘The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model were obtained from their electrochemical behavior and electrochemical data. The binding constants( K 2+ ) for Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were 8 51×10 3 L·mol -1 and 3 27×10 3 L·mol -1 , and K +s were 3 09×10 4 L·mol -1 and 5 66×10 3 L·mol -1 respectively. The spectroscopic characteristics of the complexes of Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were studied in detail. Some significant spectroelectrochemical data were obtained. The interaction of DNA with complexes was described.
文摘The title cluster compound [WS4Cu3Br(bipy)2] has been synthesized by the reaction of (NH4)2, CuBr and 2,2′ bipy in DMF solution. Single crystal X ray diffraction data show that the compound has a nest shaped structure. Nonlinear optical properties (NLO) of the cluster were investigated by a Z scan technique with a pulsed laser at 532nm. The cluster exhibits the strong NLO absorption and a self defocusing effect (effective non linear absorption coefficient, α2eff=7.3×10-11mW-1; effective non linear refractive index, n2eff=3.9×10-11esu) when measured in a 6.0×10-4mol·dm-3 DMF solution. CCDC: 200397.
文摘A new active material for ECL sensor. Ru(phen)2(phen-NICH2Br)(PF6)2 has beendesigned and synthesized. its structure was confirmed by means of IR. MS and 'H NMR. Also.some of its properties such as electrochemstry. fluorescence and ECL are reported.
文摘[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthroline（phen）. The two compounds were characterized by elemental analysis and IR spectrum analysis, respectively. Compound 1 was also characterized by single crystal X-ray diffraction analysis. For compound l, the coordination geometry around the Zn^2＋ is a distorted octahedron, with the bite angles of 76.7（3）°-77.6（4）° for all three phen ligands. Moreover, the thermal behaviors and thermal decomposition kinetics were studied and analyzed. Besides, thermal stability and safety parameters（TsADT, Tb） are 164.7 and 166.4℃ for compound 1, and 149.6 and 150.8℃ for compound 2, respectively.
