Coordination polymers of transition metal ions with polydentate imine ligands. Syntheses, materials characterization, and crystal structures of polymeric complexes of copper(i), silver(i) and zinc(ii)

Abstract

A series of new multidentate imine building blocks [NC₅H₄(R)CNCH₂CH₂NC(R)C₅H₄N (R = H 1a, R = Me 1b) and NC₅H₄CHN–NC(R)–C(R)N–NCHC₅H₄N (R = Ph 2a, R = Me 2b)] have been synthesized, aiming at the formulation of extended coordination polymers with various transition metal ions. Formation of the corresponding metal–ligand complexes has been monitored and characterized by chemical and spectroscopic techniques. X-Ray diffraction analysis of the available single crystals revealed diverse polymeric patterns of the hybrid organic–inorganic supramolecular systems. Complexation of Cu(I) with 1a and 2a yielded one-dimensional and two-dimensional polymers, respectively, with tetrahedral geometry around the metal centers. Similar reactions of Ag(I) with 1b and with 2a led to three-dimensional and two-dimensional arrays, respectively. The former contains silver ions with tetrahedral as well as square-planar coordination environments, while in the latter case the metal species bind to the ligands in a tetrahedral manner. Related syntheses of coordination compounds between 2a and bivalent metal ions produced 1-D polymers with Cd(II) and 2-D polymeric networks with Zn(II), Co(II) and Mn(II).