Thermal or photodecomposition of the classical free radical generating diazo reagent 2,2′-azobis(2-methylpropionitrile) (AIBN) was used as a source of cyanide anions in the synthesis of copper(I)-cyanide frameworks. The reported methodology utilizes the direct reduction of CuII(aa)(NN)X (aa = deprotonated amino acid, NN = bidentate nitrogen-based ligand, X = Cl or Br) complexes by AIBN/ascorbic acid to yield seven novel coordination networks. Aromatic amines were directly incorporated into 1D CuI-CN chains. In the case of the aliphatic amine tetramethylethylenediamine (TMEDA), a 3D CuI-CN framework was obtained. This novel procedure is mild, applicable to a variety of nitrogen-based ligands, and represents an efficient alternative to currently used hydrothermal or solvothermal methods. [ABSTRACT FROM AUTHOR]