Coordination polymers based on trinuclear and mononuclear copper-pyrazolate building moieties connected by fumarate or 2-methylfumarate ions

摘要

By reacting water solutions of pyrazole (Hpz) with copper(II) fumarate or 2-methylfumarate in solvothermal conditions two almost identical trinuclear triangular complexes, [Cu _3(μ _3-OH)(μ-pz) _3{R(COO) _2}(Hpz)], [R = CHCH, C(CH _3)CH], have been obtained. The two carboxylate groups of both fumarate and 2-methylfumarate show different arrangements, one acting as monotopic ligand while the other one has a ditopic behavior. Thus, in both cases, wavy 2D isomorphous Coordination Polymers (CPs), that further self-assemble through strong H-bonds into two 3D networks, have been obtained. When copper(II) 2-methylfumarate was reacted with pyrazole at r.t. the mononuclear [Cu(Hpz) _2(H _2O)(2- methylfumarate)·H _2O] complex was, in addition, obtained. In this case the bridging dianions produce instead monodimensional CPs that self-assemble into supramolecular tapes mediated by H-bond interactions, involving coordinated and crystallization water molecules. The mononuclear and trinuclear species were preliminary tested as catalysts for the oxidation of styrene by H _2O _2.