A novel three-dimensional copper(I) cyanide coordination polymer constructed from various bridging ligands:...

The cyanide ligand can act as a strong σ-donor and an effective π-electron acceptor that exhibits versatile bridging abilities, such as terminal, μ₂-C:N, μ₃-C:C:N and μ₄-C:C:N:N modes. These ligands play a key role in the formation of various copper(I) cyanide systems, including one-dimensional (1D) chains, two-dimensional (2D) layers and three-dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, μ₂-C:N and μ₃-C,C,N bridging modes have been documented so far. However, systems based on the μ₄-C:C:N:N bridging mode are relatively rare. In this work, a novel cyanide-bridged 3D Cu^I coordination framework, namely poly[(μ₂-2,2'-biimidazole-κ²N³:N^3')(μ₄-cyanido-κ⁴C:C:N:N)(μ₂-cyanido-κ²C:N)dicopper(I)], [Cu₂(CN)₂(C₆H₆N₄)]_n, (I), was synthesized hydrothermally by reaction of environmentally friendly K₃[Fe(CN)₆], CuCl₂·2H₂O and 2,2'-biimidazole (H₂biim). It should be noted that cyanide ligands may act as reducing agents to reduce Cu^II to Cu^I under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as μ₄-C:C:N:N-cyanide, μ₂-C:N-cyanide and μ₂-biimidazole. Interestingly, the [Cu₂] dimers are bridged by rare μ₄-C:C:N:N-mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu₂(μ₄-C:C:N:N)]ⁿ⁺}_n infinite chain. Furthermore, adjacent dimer-based chains are linked by μ₂-C:N bridging cyanide ligands, generating a neutral 2D wave-like (4,4) layer structure. Finally, the 2D layers are joined together via bidentate bridging H₂biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain→2D sheet→3D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid-state UV-Vis diffuse-reflectance and photoluminescence studies. The solid-state UV-Vis diffuse-reflectance spectra show that compound (I) is a wide-gap semiconductor with band gaps of 3.18 eV. The photoluminescence study shows a strong blue-green photoluminescence at room temperature, which may be associated with metal-to-ligand charge transfer.