Crystal Structures, Magnetic Properties, and Electrochemical Properties of Coordination Polymers Based on the Tetra(4-pyridyl)-tetrathiafulvalene Ligand

Seven new coordination polymers based on the redox-active tetra(4-pyridy1)-tetrathiafulvalene ligand (TTF(py)(4)) and different transition-metal ions, namely, {[Cu-(hfac)(2)] [TTF(py)(4)]center dot 2 (CH2Cl2)}(n) (1), {[Co(acac)(2)] [TTF(py())4](0.5)center dot(CHCl3)}(n) (2), {[Mn(hfac)(2)][TTF(py)(4)](0.5)}(n) (3), {[Cu-2(OAc)(4)] [TTF(py)(4)](0.5)center dot 1.5(CHCl3)center dot 0.5(H2O)center dot(CH3CN)}(n) (4), {[Mn(SCN)(2)] [TTF(py)(4)]}center dot 6(CH2Cl2)}(n) (5), {[Mn(SeCN)Cl][TTF(py)(4)]}(n) (6), and {Cu-2[TTF(py)(4)](2)center dot(ClO4)(2)center dot 2.5(CH2Cl2)center dot 1.5(CH3CN)}(n) (7), were synthesized and characterized. The tetrapyridyl ligand coordinates to metal ions in a bidentate or tetradentate fashion, forming complexes 1-7 with different structures. Complex 1 exhibits a one-dimensional chain structure. Complexes 2, 3, and 4 possess similar (4,2)-connected binodal two-dimensional networks, while complexes 5 and 6 have similar (4,4)-connected binodal two-dimensional networks with two different rings. Complex 7 shows a 2-fold interpenetrated (4,4)-connected binodal PtS-type three-dimensional framework. Meanwhile, these complexes feature diverse nonclassical hydrogen bonding interactions. In addition, magnetic and solid-state electrochemical properties for typical complexes have been studied.