A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b =...A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.展开更多
A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structur...A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structure of which was characterized by elemental analysis, IR spectrum and X-ray diffraction. Single crystal X-ray analysis indicates that this compound crystallizes in triclinic system, space group P1 with parameters: a=1.180 7(2) nm, b=1.330 0(3) nm, c=1.568 6(2) nm. 1.332 g穋m-3, F(000)=1 032, 腎=0.804+23.770C, r=0.995). CCDC: 231388.展开更多
A metal-organic Complex [Cu2(ipt)(Medpq)2]n(ipt=isophthalic acid,Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectr...A metal-organic Complex [Cu2(ipt)(Medpq)2]n(ipt=isophthalic acid,Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction.Title compound crystallizes in the monoclinic system,space group C2/c,with a=2.389 2(6) nm,b=0.709 60(18) nm,c=1.922 2(5) nm,β=108.655(3),V=3.087 8(14) nm3,C38H24Cu2 N8O4,Mr=783.73,Dc=1.686 g.cm-3,Z=4,the final R=0.055 4 and wR=0.128 5.In the crystal structure,the copper atom is three-coordinated with one carboxylate oxygen atom from carboxylate groups and two nitrogen atoms from Medpq ligand,showing a slightly distorted triangle geometry.Furthermore,it exhibits a zero-dimensional structure with ipt-Cu-medpq as building units.CCDC: 747544.展开更多
Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2·1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2·H2O(2),[Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2·H2O(4) a...Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2·1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2·H2O(2),[Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2·H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively.The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt==A.exp(-E/RT).(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A·exp(-E/RT)·.(1-α)2, which corresponds to the mechanism of "the second-order chemical reartion".展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
基金Project(21001118)supported by National Natural Science Foundation of ChinaProject(12JJ3016)supported by Natural Science Foundation of Hunan Province,China
文摘A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.
文摘A Cu(Ⅰ) complex [Cu(INHPy)(PPh3)2] ·(ClO4)·0.75(C2H5OH) was obtained through self-assembly between [Cu(PPh3)2(MeCN)2]ClO4 and Schiff base 2-pyridylcarboxaldehyde isonicotinoyl hadrazone(INHPy), the structure of which was characterized by elemental analysis, IR spectrum and X-ray diffraction. Single crystal X-ray analysis indicates that this compound crystallizes in triclinic system, space group P1 with parameters: a=1.180 7(2) nm, b=1.330 0(3) nm, c=1.568 6(2) nm. 1.332 g穋m-3, F(000)=1 032, 腎=0.804+23.770C, r=0.995). CCDC: 231388.
文摘A metal-organic Complex [Cu2(ipt)(Medpq)2]n(ipt=isophthalic acid,Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction.Title compound crystallizes in the monoclinic system,space group C2/c,with a=2.389 2(6) nm,b=0.709 60(18) nm,c=1.922 2(5) nm,β=108.655(3),V=3.087 8(14) nm3,C38H24Cu2 N8O4,Mr=783.73,Dc=1.686 g.cm-3,Z=4,the final R=0.055 4 and wR=0.128 5.In the crystal structure,the copper atom is three-coordinated with one carboxylate oxygen atom from carboxylate groups and two nitrogen atoms from Medpq ligand,showing a slightly distorted triangle geometry.Furthermore,it exhibits a zero-dimensional structure with ipt-Cu-medpq as building units.CCDC: 747544.
文摘Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2·1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2·H2O(2),[Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2·H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively.The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt==A.exp(-E/RT).(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A·exp(-E/RT)·.(1-α)2, which corresponds to the mechanism of "the second-order chemical reartion".
