Tuning of valence States, bonding types, hierarchical structures, and physical properties in copper/halide/isonicotinate system.

Seven cupric halide coordination polymers, namely [Cu5(OH)3Br3(ina)4] (1), [Cu5(OH)3Cl3(ina)4] (2), [Cu2(OH)Cl(ina)2] (3), [Cu3(OH)2Cl2(ina)2]·2H2O (4), [Cu3(OH)2Br2(ina)2]·2H2O (5), [Cu2Cl2(ina)2(H2O)2] (6), [Cu2Cl(ina)2(gca)(H2O)] (7), cupric complex templated cuprous halide [Cu(II)(Me-ina)2(H2O)][Cu(I)5Br7] (8), and organic templated cuprous halide Me2-ina[Cu2Br3] (9) (Hina = isonicotinic acid), were prepared from the starting materials of cupric halide and Hina via fine-tuning solvothermal reactions. According to valence states of copper, 1-7 are copper(II) complexes, 8 is a mixed-valent Cu(I,II) complex, while 9 is a Cu(I) compound. According to bonding types of halides, nine complexes can be classified as three types: complexes 1-3 include only normal X-Cu bond (X = halide); complexes 4-7 include normal X-Cu bond and X···Cu weak bond; complexes 8 and 9 include normal X-Cu bond and X···H-C halogen hydrogen bonds. Complexes 1 and 2 are isomorphic three-dimensional (3D) pcu topological metal organic frameworks (MOFs) with butterfly-like Cu4(μ3-OH)2X2 and steplike Cu6(μ3-OH)4 cores as nodes, showing strong ferromagnetic couplings. Complex 3 also is a pcu topological MOF with only butterfly-like Cu4(μ3-OH)2Cl2 clusters as nodes, presenting spin canting antiferromagnetic behavior. Isostructural 4 and 5 are Cu3(OH)2 clusters based two-dimensional (2D) (4,4) layers, which are extended into 3D eight-connected networks via weak Cu···X bonds, showing ferromagnetic coupling. Antiferromagnetic 6 is a simple one-dimensional coordination polymer, which is extended via weak Cu···Cl bonds into 3D (3,4)-connected networks. Paramagnetic 7 is a ladderlike polymer, which is extended into 2D (3,4)-connected layer via weak Cu···Cl bonds. The syntheses of polymeric cupric complexes 1-7 mainly result from differences in reactant ratio and pH value. Utilization of reducing methanol generated novel cubane-containing [Cu5Br7](2-) chain templated by paddlewheel-like [Cu(II)(Me-ina)2](2+) 8 and face-shared dimer-containing [Cu2Br3](-) chain templated by N-methylated and O-esterificated Me2-ina 9. Complex 9 exhibits a strong red emission and a weaker green emission upon excitation.