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.