Controlled interpenetration of 44networks: syntheses and structures of two Cu3-cluster coordination polymers

Abstract

The reaction of copper nitrate and triethanolamine with benzene-1,4-dicarboxylic acid (bdcH2) or 4,4'-[1,4-phenylenebis(oxy)]dibenzoic acid (podaH2) leads to the formation of poly[bis(μ4-benzene-1,4-dicarboxylato-κ4O1:O1':O4:O4)bis{μ2-[bis(2-hydroxyethyl)amino]ethanolato-κ4N,O,O',O'':κO}tricopper(II)], [Cu3(C8H4O4)2(C6H14NO3)2] or [Cu3(μ4-bdc)2(teaH2)2] (I), and poly[bis{μ4-4,4'-[1,4-phenylenebis(oxy)]dibenzoato-κ4O:O':O'':O''}bis{μ2-[bis(2-hydroxyethyl)amino]ethanolato-κ4N,O,O',O'':κO}tricopper(II)], [Cu3(C20H12O6)2(C6H14NO3)2] or [Cu3(μ4-poda)2(teaH2)2], (II). The two representative compounds contain a well-established Cu3 cluster supporting a given 44 network. The ligand length is the underlying factor that controls the degree of interpenetration. Controlled interpenetration can be facile to realise by elongating protocols. Compound I shows a non-interpenetrating 44 network, whereas II features a threefold interpenetrating network. Furthermore, similar hydrogen-bond interactions extend the different interpenetrating 44 networks into three-dimensional supramolecular topologies. Variable-temperature magnetic studies showed a ferromagnetic coupling behaviour in the two complexes.