Controlled interpenetration of 4 4 networks: syntheses and structures of two Cu 3 ‐cluster coordination polymers

The reaction of copper nitrate and triethanolamine with benzene‐1,4‐dicarboxylic acid (bdcH 2 ) or 4,4′‐[1,4‐phenylenebis(oxy)]dibenzoic acid (podaH 2 ) leads to the formation of poly[bis(μ 4 ‐benzene‐1,4‐dicarboxylato‐κ 4 O 1 : O 1′ : O 4 : O 4 )bis{μ 2 ‐[bis(2‐hydroxyethyl)amino]ethanolato‐κ 4 N , O , O ′, O ′′:κ O }tricopper(II)], [Cu 3 (C 8 H 4 O 4 ) 2 (C 6 H 14 NO 3 ) 2 ] or [Cu 3 (μ 4 ‐bdc) 2 (teaH 2 ) 2 ] ( I ), and poly[bis{μ 4 ‐4,4′‐[1,4‐phenylenebis(oxy)]dibenzoato‐κ 4 O : O ′: O ′′: O ′′}bis{μ 2 ‐[bis(2‐hydroxyethyl)amino]ethanolato‐κ 4 N , O , O ′, O ′′:κ O }tricopper(II)], [Cu 3 (C 20 H 12 O 6 ) 2 (C 6 H 14 NO 3 ) 2 ] or [Cu 3 (μ 4 ‐poda) 2 (teaH 2 ) 2 ], ( II ). The two representative compounds contain a well‐established Cu 3 cluster supporting a given 4 4 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 4 4 network, whereas II features a threefold interpenetrating network. Furthermore, similar hydrogen‐bond interactions extend the different interpenetrating 4 4 networks into three‐dimensional supramolecular topologies. Variable‐temperature magnetic studies showed a ferromagnetic coupling behaviour in the two complexes.