Tetrathiafulvalene-Tetracarboxylate: An Intriguing Building Block with Versatility in Coordination Structures and Redox Properties

The synthesis of the transition metal coordination polymers containing a tetrathiafulvalene (TTF) moiety substituted with a tetracarboxylate group of the formulas [Mn(L)(0.5)(phen)(H2O)(2)](n)center dot nH(2)O (1), [Mn(L)(0.5)(bpy)](n)center dot nH(2)O (2), [Mn(L)(0.5)(bpy)(CH3OH)](n)center dot 2nH(2)O (3), and [Cu(L)(0.5)(bpy)(DMF)](n)center dot n(DMF) (4) (L4- = TTF-tetracarboxylate; phen = 1,10-phenanthroline; bpy = 2,2'-bipyridine) is reported. Complex 1 is a two-dimensional (2-D) coordination polymer constructed of infinite carboxylate bridged Mn(II) chains and TTF moiety linkages. Complex 2 possesses a 3-D polymeric structure formed by infinite -Mn-(O-C-O)(2)-Mn- bridged one-dimensional (1-D) chains, which are further coordinated by TTF-tetracarboxylate ligands of two different orientations. Both complexes 3 and 4 show 1-D extended chain structures but are constituted by different dinuclear metal(II) units with a -Mn-(O-C-)(2)-Mn- bridge in 3 and a -Cu-(O)(2)-Cu bridge in 4. Electrochemical study of the solid-state compounds attests to the redox activity of the coordination system. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in complexes 3 and 4, while in 1, the paramagnetic metallic centers are isolated, in agreement with the solid-state structure.