Anion Tuning of Cu(II)/4,4′‐Bi‐1,2,4‐Triazole Coordination Polymers

Abstract

AbstractNine CuII coordination compounds based on 4,4′‐bi‐1,2,4‐triazole (btr), [Cu2(N‐btr)2(OAc)4]·4H2O (1), [Cu(N1,N1′‐btr)2(H2O)2][CdBr4(H2O)]·3H2O (2), [Cu(N1,N1′‐btr)2(H2O)2]S2O6·4H2O (3), [Cu(N1,N1′‐btr)2(H2O)2](NO3)2·2H2O (4), [Cu2(N1,N1′‐btr)2(μ3‐btr)2(NO3)2](NO3)2·2H2O (5), [Cu(N1,N1′‐btr)2(DMF)2](NO3)2·2C2H5OH (6), [Cu(N1,N1′‐btr)3](CF3CO2)2 (7), [Cu(N1,N1′‐btr)2(N‐btr)2](CCl3CO2)2·5H2O (8), [Cu3(μ2‐OH)2(μ4‐btr)(μ3‐btr)2(N1,N1′‐btr)(H2O)(CF3CO2)](CF3CO2)3·4H2O (9), were synthesized by reaction of btr with the corresponding CuII salts in aqueous or DMF/ethanol solution and their structures were established with single X‐ray diffraction. The coordination behavior of btr, which changes from simple monodentate, to N1,N1′‐bi‐, tri‐ and tetradentate binding modes, and the influence of the counteranions lead to a structural variety of the coordination compounds, ranging from molecular “Chinese lanterns” of type 1, through 2D square grids (2–4, 6, 8) and 3D octahedral networks (7), to 3D eight‐connected frameworks (5, 9) that based on the dinuclear [Cu2(trz)2]4+ and linear trinuclear [Cu3(μ2‐OH)2(H2O)2]4+ units as nodes.