By using solvothermal method,two novel coordination polymers based on 4-（4-carboxyphen-yl）-1,2,4-triazole（Hcpt） and Zn（Ⅱ） cations,[Zn（cpt）（OH）]_n·n H_2O（FJU-32） and [Zn（cpt）（atrz）]n（FJU-33）（Ha...By using solvothermal method,two novel coordination polymers based on 4-（4-carboxyphen-yl）-1,2,4-triazole（Hcpt） and Zn（Ⅱ） cations,[Zn（cpt）（OH）]_n·n H_2O（FJU-32） and [Zn（cpt）（atrz）]n（FJU-33）（Hatrz = 3-amino-1,2,4-triazolate）,were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441（3）,b = 23.0384（19）,c = 11.8562（10） ？,β = 99.069（8）o,V = 1009.91（15） ？3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F（000） = 916,μ（MoKα） = 2.439 mm^（-1）,Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections（I 〉 2σ（I））,and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483（5）,b = 9.9922（3）,c = 9.8403（3） ？,β = 100.756（4）°,V = 1231.47（7） ？~3,Dc = 1.816 g/cm^3,C_（11）H_9N_7O_2Zn,Mr = 336.62,F（000） = 680,μ（Cu Kα） = 2.957 mm^（-1）,Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections（I 〉 2σ（I））,and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn（Ⅱ） is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn（atrz）] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.展开更多
基金Financially supported by the National Natural Science Foundation of China(21207018,21273033,21203024 and 21573042)Fujian Science and Technology Department(2014J06003,2014H6007 and 2016J01046)+2 种基金college students'innovative training program(201510394008,201510394055)the supports from Recruitment Program of Global Young Experts,Program for New Century Excellent Talents in University(NCET-10-0108)the Award‘Minjiang Scholar Program’in Fujian Province
文摘By using solvothermal method,two novel coordination polymers based on 4-（4-carboxyphen-yl）-1,2,4-triazole（Hcpt） and Zn（Ⅱ） cations,[Zn（cpt）（OH）]_n·n H_2O（FJU-32） and [Zn（cpt）（atrz）]n（FJU-33）（Hatrz = 3-amino-1,2,4-triazolate）,were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441（3）,b = 23.0384（19）,c = 11.8562（10） ？,β = 99.069（8）o,V = 1009.91（15） ？3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F（000） = 916,μ（MoKα） = 2.439 mm^（-1）,Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections（I 〉 2σ（I））,and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483（5）,b = 9.9922（3）,c = 9.8403（3） ？,β = 100.756（4）°,V = 1231.47（7） ？~3,Dc = 1.816 g/cm^3,C_（11）H_9N_7O_2Zn,Mr = 336.62,F（000） = 680,μ（Cu Kα） = 2.957 mm^（-1）,Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections（I 〉 2σ（I））,and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn（Ⅱ） is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn（atrz）] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.
