Synthesis, Structure and Photoluminescent Studies of a Novel Supramolecular [Ag(phen)(CN)]·(phen) Complex

A novel AgI complex [Ag(phen)(CN)]·(phen) (phen = 1,10‐phenanthroline) has been solvothermally synthesized and characterized by X‐ray diffraction. The crystal packing reveals unprecedented threefold interpenetrating three‐dimensional four‐connected networks self‐assembled through C‐H···N hydrogen bonds and π···π stacking interactions, which are stabilized by strong C‐H···π interactions between the three independent networks. The photoluminescent properties have been investigated by molecular orbital (MO) calculations, showing that the luminescent properties of the complex in the solid state are due to both a πL⇄πL* transition of the uncoordinated phen species and metal‐to‐ligand charge transfer (MLCT), admixed with the cyanide‐to‐ligand charge transfer (XLCT) of the [Ag(phen)(CN)] species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)