Progressive Structure Designing and Property Tuning of Manganese(II) Coordination Polymers with the Tetra(4-pyridyl)-tetrathiafulvalene Ligand

Three new Mn(II) coordination polymers (CPs) derived from the redox-active tetra(4-pyridyl)-tetrathiafulvalene ligand (TTF(py)4), namely, {[MnCl2(TTF(py)4)]·4CH2Cl2·CH3OH}n (1), {[Mn(N3)(TTF(py)4)]·(ClO4)·2CHCl3·CH3OH)}n (2), and {[Mn(dca)2(TTF(py)4)0.5]·CH3OH}n (3) (dca = dicyanamide), were synthesized and characterized. Their topology and dimensionality are dependent on the counteranion used: Cl– forms a two-dimensional network, N3– induces a (4,6)-connected binodal sqc11-type three-dimensional (3D) framework, while dca results in a 2-fold interpenetrated (4,6)-connected binodal sqc173-type topological 3D framework. All compounds exhibit redox activity and display antiferromagnetic interactions. A single-crystal-to-single-crystal transformation from 2 to 2′ induced by solvent exchange was observed and structurally characterized.