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-pyridyl)-tetrathiafulvalene ligand (TTF­(py)4) and different transition-metal ions, namely, {[Cu­(hfac)2]­[TTF­(py)4]·2­(CH2Cl2)} n (1), {[Co­(acac)2]­[TTF­(py)4]0.5·(CHCl3)} n (2), {[Mn­(hfac)2]­[TTF­(py)4]0.5} n (3), {[Cu2(OAc)4]­[TTF­(py)4]0.5·1.5­(CHCl3)·0.5­(H2O)·(CH3CN)} n (4), {[Mn­(SCN)2]­[TTF­(py)4]·6­(CH2Cl2)} n (5), {[Mn­(SeCN)­Cl]­[TTF­(py)4]} n (6), and {Cu2[TTF­(py)4]2·(ClO4)2·2.5­(CH2Cl2)·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.