Reaction of 3-（pyridin-2-yl）-imidazo[1,5-a]pyridine （HPIP）, CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] （1） and [HLCuC1]E[C...Reaction of 3-（pyridin-2-yl）-imidazo[1,5-a]pyridine （HPIP）, CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] （1） and [HLCuC1]E[CuCI2]2[CuCI3].2H20 （2） （L = 1,1＇-（pyridin-2- ylmethylene）bis[3-（pyridin-2-yl）imidazo[1,5-a]pyridine]） simultaneously. The ligand L was generated via in situ metal-ligand reaction between HPIP and picolinaldehyde. When CuCI2·2H20 was replaced by CuC1, the 2：1：1（HPIP：picolinaldehyde：CuCI） reaction afforded complex [CuaL2CI2][CuCI2]·2H20 （3） and the analogous 2：1：3 reaction generated compound [CuaL2][CuCI2]3 （4）. Complexes 1 and 2 are Cun/CuI mixed-valence compounds. Complexes 1-4 display four various structures. It is found that the formation of the L ligand is controlled by CH3COOH. This work reveals that the structures of complexes 1-4 could be rationally tuned via the inclusion of CH3COOH in the reaction systems, the proper selection of different starting materials and the dexterous adjustment of the ratio of the starting materials.展开更多
A new CuII complex with a diazamesocyclic ligand based on 1,4-diazacycloheptane (DACH) and functionalized with two additional quinoline donor groups, namely N,N-bis(quinolin-8- ylmethyl)-1,4-diazacycloheptane L, has b...A new CuII complex with a diazamesocyclic ligand based on 1,4-diazacycloheptane (DACH) and functionalized with two additional quinoline donor groups, namely N,N-bis(quinolin-8- ylmethyl)-1,4-diazacycloheptane L, has been synthesized and characterized. X-ray diffraction analysis at room temperature indicates that the title complex [CuLCl](ClO4) 1 (C25H26Cl2N4O4Cu, Mr = 580.94) crystallizes in triclinic, space group P1 with a = 9.589(3), b = 10.857(4), c = 12.724(5) ? a = 98.168(7), b = 106.945(7), g = 101.248(7), V = 1214.6(8) 3, Z = 2, Dc = 1.588 g/cm3, F(000) = 598 and m(MoKa) = 1.161 mm-1. The final R = 0.0479 and wR = 0.0985 with 4267 independent reflections. In the mononuclear CuII complex, the CuII center is pentacoordinated to four nitrogen donors of the ligand and one axial chloride anion, taking a coordination sphere in the midst of the ideal square- pyramid and trigonal bipyramid.展开更多
基金Supported by NNSFC(21272167)the Priority Academic Program Development of Jiangsu Higher Education Institution,and KLSLRC(KLSLRC-KF-13-HX-1)
文摘Reaction of 3-（pyridin-2-yl）-imidazo[1,5-a]pyridine （HPIP）, CuCi2·2H20 and picolinaldehyde in the mixture of CHaCOOH and EtOH under solvothermal conditions gave complexes [LCuCI][CuECI3] （1） and [HLCuC1]E[CuCI2]2[CuCI3].2H20 （2） （L = 1,1＇-（pyridin-2- ylmethylene）bis[3-（pyridin-2-yl）imidazo[1,5-a]pyridine]） simultaneously. The ligand L was generated via in situ metal-ligand reaction between HPIP and picolinaldehyde. When CuCI2·2H20 was replaced by CuC1, the 2：1：1（HPIP：picolinaldehyde：CuCI） reaction afforded complex [CuaL2CI2][CuCI2]·2H20 （3） and the analogous 2：1：3 reaction generated compound [CuaL2][CuCI2]3 （4）. Complexes 1 and 2 are Cun/CuI mixed-valence compounds. Complexes 1-4 display four various structures. It is found that the formation of the L ligand is controlled by CH3COOH. This work reveals that the structures of complexes 1-4 could be rationally tuned via the inclusion of CH3COOH in the reaction systems, the proper selection of different starting materials and the dexterous adjustment of the ratio of the starting materials.
基金This work was financially supported by NNSFC (No. 29971019)
文摘A new CuII complex with a diazamesocyclic ligand based on 1,4-diazacycloheptane (DACH) and functionalized with two additional quinoline donor groups, namely N,N-bis(quinolin-8- ylmethyl)-1,4-diazacycloheptane L, has been synthesized and characterized. X-ray diffraction analysis at room temperature indicates that the title complex [CuLCl](ClO4) 1 (C25H26Cl2N4O4Cu, Mr = 580.94) crystallizes in triclinic, space group P1 with a = 9.589(3), b = 10.857(4), c = 12.724(5) ? a = 98.168(7), b = 106.945(7), g = 101.248(7), V = 1214.6(8) 3, Z = 2, Dc = 1.588 g/cm3, F(000) = 598 and m(MoKa) = 1.161 mm-1. The final R = 0.0479 and wR = 0.0985 with 4267 independent reflections. In the mononuclear CuII complex, the CuII center is pentacoordinated to four nitrogen donors of the ligand and one axial chloride anion, taking a coordination sphere in the midst of the ideal square- pyramid and trigonal bipyramid.
