Influence Of The Metal Ion On The Topology And Interpenetration Of Pyridylvinyl(Benzoate) Based Metal-Organic Frameworks

A family of four M(II)-metal-organic frameworks of general formula {[M-x(pvb)(2x)]y(dmf)}(n) (M = Cu, 1; M = Co, 2; M = Ni, 3; M = Mn, 4), based on the bis{4-[2-(4-pyridyl)ethenyl]} benzoic acid (Hpvb) ligand, were obtained. 1 exhibits a 5-fold interpenetrated lvt framework, 2 and 3 a 7-fold interpenetrating dia framework, and 4 a 2-fold interpenetrated dmc framework. Magnetic properties of 1-4 have been investigated. 1 was analyzed by a Curie-Weiss model, while 2 and 3 where analyzed by a zero-field splitting model due to the very long metal-metal distances, which results in very weak antiferromagnetic interactions. The coupling pathway in 4 was done by carboxylate bridges instead of the pvb pathway, affording a short metal-metal separation that was analyzed by a isotropic Heisenberg spin Hamiltonian for a linear trinuclear Mn(II) cluster. The different metal coordination modes and geometries, along with template effects induced by the solvent, play an important role in the formation of distinctive structural topologies.