合成和表征了1个新的钌(Ⅱ)配合物[R u(bpy)2(dpapz)](C lO4)2,其中bpy=2,2′-联吡啶,dpapz=联吡啶并[3,2-a:2,′3-′c]-6-氮杂-吩嗪.通过紫外可见光谱、荧光光谱、与溴化乙锭的竞争键合实验和粘度测量研究了该配合物与小牛胸腺DNA的键...合成和表征了1个新的钌(Ⅱ)配合物[R u(bpy)2(dpapz)](C lO4)2,其中bpy=2,2′-联吡啶,dpapz=联吡啶并[3,2-a:2,′3-′c]-6-氮杂-吩嗪.通过紫外可见光谱、荧光光谱、与溴化乙锭的竞争键合实验和粘度测量研究了该配合物与小牛胸腺DNA的键合性质,并研究了该配合物的紫外可见光谱和荧光光谱的溶剂变色性质.结果表明,该配合物是具有键合常数Kb=6.9×105L/m o l(50 mm o l/L N aC l)的DNA嵌入键合试剂和优良的荧光溶剂传感分子.展开更多
THE conversion of visible light to electricity using semiconductors as light absorbers has beenan important area of research for many years. In the 1970s, highly efficient photovoltaiccells based on silicon were devel...THE conversion of visible light to electricity using semiconductors as light absorbers has beenan important area of research for many years. In the 1970s, highly efficient photovoltaiccells based on silicon were developed (the light-to-electrical conversion efficiency≥25%),which provides energy to aircrafts. Then semiconductor liquid-junction photoelectrochemicalcell started to be investigated. Generally speaking, highly efficient liquid-junction photoelec-trochemical solar cells can be obtained by using semiconductors such as Si, GaAs and WSe.(band gap≈(1.3±0.3) eV). Conversion efficiencies over 15% have been acquired on solarcells consisting of single crystals of Si or GaAs. But the serious photocorrosion and high展开更多
Nonionic water soluble complex Ru 3(CO) 9(PETPP) 3 with the function of thermoregulated phase transfer catalysis was prepared. The catalytic activity and the recycle effect of Ru 3(CO) 9(PETPP) 3 for hydrogenation of ...Nonionic water soluble complex Ru 3(CO) 9(PETPP) 3 with the function of thermoregulated phase transfer catalysis was prepared. The catalytic activity and the recycle effect of Ru 3(CO) 9(PETPP) 3 for hydrogenation of styrene in aqueous/organic biphase catalysis system were studied. In addition, effects of reaction temperature, hydrogen pressure and reaction time were also investigated. The results showed that the reaction takes place mainly in organic phase at higher temperature (80 ℃). Under the conditions of θ =80 ℃, p (H 2)=2 MPa and t =3 h, both the PhCH∶CH 2 conversion and PhC 2H 5 selectivity are 100%. The PhCH∶CH 2 conversion is still 98 2% after reuse of the catalyst for 20 times. The catalytic performance of Ru 3(CO) 9(TPPTS) 3, Ru 3(CO) 9(PETPP) 3, Ru 3(CO) 9(TPPMS) 3 and Ru 3(CO) 9(TPP) 3 for biphase hydrogenation of styrene was compared. The experimental results for Ru 3(CO) 9(PETPP) 3 verified that there is a thermoregulated phase transfer catalysis process in the reaction system.展开更多
A new ruthenium（Ⅱ） complex,[Ru（bpy）2bdpq](ClO4)2,where bpy=2,2′-bipyridine,（bdpq=2-（benzoxazol-2-yl）-dipyrido） [2,3-f: 2′,3′-h]quinoxaline,was synthesized and characterized by IR,（）1H NMR,MALDI-TOF MS,an...A new ruthenium（Ⅱ） complex,[Ru（bpy）2bdpq](ClO4)2,where bpy=2,2′-bipyridine,（bdpq=2-（benzoxazol-2-yl）-dipyrido） [2,3-f: 2′,3′-h]quinoxaline,was synthesized and characterized by IR,（）1H NMR,MALDI-TOF MS,and elemental analysis.The electronic absorption and emission spectral titrations with calf thymus DNA,steady-state emission quenching by [Fe（CN）6]4-,and viscosity measurements were carried out to study the binding of [Ru（bpy）2bdpq](ClO4)2 with the DNA.The results indicate that the（Ru（Ⅱ）） complex acts as a DNA intercalator with a binding constant of（1.9±0.1）×106 L/mol at 50 mmol/L NaCl,and can serve as a good "DNA molecular light switches" with a luminescence enhancement factor of 180.展开更多
A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to e...A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to explore their electronic structures, absorption, and emissions as well as the solvatochrom-ism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1-3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is con-tributed by π*(L). Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing elec-tron-withdrawing group on ligand L will induce remarkable solvatochromism.展开更多
文摘合成和表征了1个新的钌(Ⅱ)配合物[R u(bpy)2(dpapz)](C lO4)2,其中bpy=2,2′-联吡啶,dpapz=联吡啶并[3,2-a:2,′3-′c]-6-氮杂-吩嗪.通过紫外可见光谱、荧光光谱、与溴化乙锭的竞争键合实验和粘度测量研究了该配合物与小牛胸腺DNA的键合性质,并研究了该配合物的紫外可见光谱和荧光光谱的溶剂变色性质.结果表明,该配合物是具有键合常数Kb=6.9×105L/m o l(50 mm o l/L N aC l)的DNA嵌入键合试剂和优良的荧光溶剂传感分子.
文摘THE conversion of visible light to electricity using semiconductors as light absorbers has beenan important area of research for many years. In the 1970s, highly efficient photovoltaiccells based on silicon were developed (the light-to-electrical conversion efficiency≥25%),which provides energy to aircrafts. Then semiconductor liquid-junction photoelectrochemicalcell started to be investigated. Generally speaking, highly efficient liquid-junction photoelec-trochemical solar cells can be obtained by using semiconductors such as Si, GaAs and WSe.(band gap≈(1.3±0.3) eV). Conversion efficiencies over 15% have been acquired on solarcells consisting of single crystals of Si or GaAs. But the serious photocorrosion and high
文摘Nonionic water soluble complex Ru 3(CO) 9(PETPP) 3 with the function of thermoregulated phase transfer catalysis was prepared. The catalytic activity and the recycle effect of Ru 3(CO) 9(PETPP) 3 for hydrogenation of styrene in aqueous/organic biphase catalysis system were studied. In addition, effects of reaction temperature, hydrogen pressure and reaction time were also investigated. The results showed that the reaction takes place mainly in organic phase at higher temperature (80 ℃). Under the conditions of θ =80 ℃, p (H 2)=2 MPa and t =3 h, both the PhCH∶CH 2 conversion and PhC 2H 5 selectivity are 100%. The PhCH∶CH 2 conversion is still 98 2% after reuse of the catalyst for 20 times. The catalytic performance of Ru 3(CO) 9(TPPTS) 3, Ru 3(CO) 9(PETPP) 3, Ru 3(CO) 9(TPPMS) 3 and Ru 3(CO) 9(TPP) 3 for biphase hydrogenation of styrene was compared. The experimental results for Ru 3(CO) 9(PETPP) 3 verified that there is a thermoregulated phase transfer catalysis process in the reaction system.
文摘A new ruthenium（Ⅱ） complex,[Ru（bpy）2bdpq](ClO4)2,where bpy=2,2′-bipyridine,（bdpq=2-（benzoxazol-2-yl）-dipyrido） [2,3-f: 2′,3′-h]quinoxaline,was synthesized and characterized by IR,（）1H NMR,MALDI-TOF MS,and elemental analysis.The electronic absorption and emission spectral titrations with calf thymus DNA,steady-state emission quenching by [Fe（CN）6]4-,and viscosity measurements were carried out to study the binding of [Ru（bpy）2bdpq](ClO4)2 with the DNA.The results indicate that the（Ru（Ⅱ）） complex acts as a DNA intercalator with a binding constant of（1.9±0.1）×106 L/mol at 50 mmol/L NaCl,and can serve as a good "DNA molecular light switches" with a luminescence enhancement factor of 180.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20573042, 20703015, and 20333050)
文摘A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to explore their electronic structures, absorption, and emissions as well as the solvatochrom-ism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1-3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is con-tributed by π*(L). Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing elec-tron-withdrawing group on ligand L will induce remarkable solvatochromism.
