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)

A series of new multidentate imine building blocks [NC₅H₄(R)C=NCH₂CH₂N=C(R)C ₅H₄N (R = H 1a, R = Me 1b) and NC₅H₄CH=N-N=C(R)-C(R)=N-N=CHC₅H₄N (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).