A Series of One‐ to Three‐Dimensional Copper Coordination Polymers Based on N‐Heterocyclic Ligands

A family of copper coordination polymers containing different N‐heterocyclic ligands, namely [Cu(CN)(dmpyz)] n ( 1 ),[Cu 2 (CN) 2 (imz)] n ( 2 ), [Cu 3 (CN)(trz) 2 ] n ( 3 ), [Cu 6 (CN) 6 (dmtrz) 3 ] n ( 4 ), [Cu 2 (CN)(5‐metta)] n ( 5 ), [Cu 2 (CN)(5‐phtta)] n ( 6 ), and {[Cu 6 (CN) 6 (dmtrz)] 2 [Cu 2 (CN) 2 (dmtrz) 2 ]} n ( 7 ) has been prepared and structurally characterized by X‐ray crystallography. The crystal structures of 1 and 2 are 1D chain frameworks. Compound 3 is a twofold interpenetrating 2D supramolecular framework in which the cyanide groups act as bridging ligands to link the copper centers into an unusual bilayer motif with large channels. Compounds 4 – 6 all possess 3D networks. Compound 4 is constructed by two parts: 2D rectangular‐grid layers and {Cu 2 (CN) 2 (dmtrz) 2 } building blocks. Compound 5 is built up by X‐shaped chains that connect each other in an ABAB arrangement to generate the3D network. The structure of 6 is a 3D network includingone‐dimensional square‐grid channels, with a shortest Cu2 ··· Cu2A (A: – x + 1, – y + 1, – z ) distance of about 2.347(1) Å. Compound 7 features a peculiar 3D + 1D network in which 1D guest metal‐organic polymer chains are filled in an unusual 3D architecture constructed by double helical host tubes. Compounds 1 – 7 show a systematic variation in dimensionality from 1D to 3D to 3D + 1D. The luminescence properties of these compounds have been also studied. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)