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Hydrothermal reactions of CuCN, K3[Fe(CN)6] with 2,2′-bipyridine, 1,10-phenanthroline or 2,6-bis(1,2,4-triazolyl)pyridine (btp) afford three coordination polymers, [Cu7(CN)7(bipy)2] n (1), [Cu2(CN)2(phen)] n (2) and [Cu3(CN)3(btp)] n (3). Complex 1 displays 1D polymeric ribbons which are assembled through Cu ··· Cu and π–π stacking interactions into a 3D framework. Complex 2 shows a 1D zigzag chain structure in which phen is a side ligand. In 3, the copper cyanide 2D polymeric networks are connected by tridentate btp to form a 3D metal-organic framework. These coordination polymers exhibit strong fluorescent emissions in the solid state.

Hydrothermal reaction of CuCN, K 3 [Fe(CN) 6 ] with 4-(6-amino-2-pyridyl)-1,2,4-triazole (apt) afforded a coordination polymer [Cu 7 (CN) 7 (apt) 2 ] n ( 1 ), while solvothermal reaction of CuSCN with apt in acetonitrile afforded a coordination polymer [Cu 2 (SCN) 2 (apt)] n ( 2 ). Complex 1 shows two-dimensional polymeric network with large hexagonal channels constructing by CuCN chains and tridentate apt ligands. Complex 2 shows two-dimensional polymeric framework assembled by ladder-like [Cu(SCN)] n chains and bidentate apt ligands, in which thiocyanate acts as a tridentate bridging ligand. Both polymers are thermal stable and strong fluorescent in the solid state.

Two new cyano-bridged bimetallic complexes, [Cu(TAAB)Fe(CN) 5 (NO)]·2H 2 O ( 1 ) and [Mn(bpy) 2 (H 2 O)Fe(CN) 5 (NO)]·H 2 O ( 2 ) (where TAAB = tetrabenzo[ b , f , j , n ][1,5,9,l3]tetraaza-cyclohexadecine and bpy = 2,2′-bipyridine), have been synthesized and characterized by elemental analyses, IR spectra and TG-DSC analyses. Single crystal X-ray structure analyses revealed that the complex 1 has a cyano-bridged binuclear structure in which Cu(II) center is coordinated by tetraazacyclic TAAB ligand to form an intriguing saddle-shaped structure, and Fe(II) center is in an octahedral coordination environment with nitrosyl group trans to the cyano-bridge. In complex 2 , Mn(II) center is cis six-coordinated and linked to nitroprusside though a bridging cyanide group to form a binuclear structure, while the nitrosyl group is cis to the cyano-bridge. The thermal stabilities of both complexes were investigated, which shows the nitrosyl and cyanide groups of nitroprusside released by two-steps in the temperature range of 200–380 °C.

Hydrothermal reaction of CuCN, K3[Fe(CN)6] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu3(CN)3(phen)]n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.