Near-IR absorption due to supramolecular electronic interaction in an extended 3D hydrogen-bonding network material: synthesis, crystal structure and properties of [4,4 '-H(2)bpy][Cu(mnt)(2)]

摘要

The synthesis and single-crystal X-ray structure of an ion-pair complex, [4,4'-H(2)bpy][Cu(mnt)(2)] (1), is described. In the crystal structure. the interactions between anions and cations via bifurcated (bpyN)-H...(NC-mnt)(2) hydrogen bonds give rise to a three-dimensional supramolecular network having well-defined channels. Complex I exhibits two redox waves at +0.44 and -0.36 V (versus SCE) in dimethylformamide corresponding to the Cu(mnt)(2)](1-)/Cu(mnt)(2)]2(-) and [4,4'-H(2)bpy](2+)/[4,4'-H(2)bpy](1+) couples respectively. The near-IR absorption at 1225 nm in the solid state has been attributed to the charge transfer from the copper dithiolate anion, [Cu(mnt)(2)](2-), to the bipyridinium cation, [4,4'-H(2)bpy](2+). (C) 2004 Elsevier Ltd. All rights reserved.