The design, assembly, properties and crystal structure of one-dimensional polymeric cyanide-bridged nickel(II)/nickel(II) complexes

Four novel one-dimensional polymeric complexes {[Ni(pn)(2)Ni(CN4]. H2O}(n) (1), {[Ni(tn)(2)Ni(CN)(4)]. H2O}(n) (2), {[Ni(dien)Ni(CN)(4)] (H2O)(2))}(n) (3) and {[Ni(trien)Ni(CN)(4)]. H2O}(n) (4) (where pn = 1,2-diaminopropane, tn = 1,3-diaminopropane, dien = diethylenetriamine and trien = triethylene tetraamine) have been synthesized by the reaction of [Ni(L)(m)](2+) with [N i(CN)(4)](2-) in aqueous solution. Their properties have been studied by IR spectra, UV-Vis spectra, cyclic voltammetry and variable temperature magne tic susceptibility measurements. The molecular structure of complex I has b een determined by X-ray diffraction, consisting of a one-dimensional polyme ric chain -Ni(pn)(2)-NC-Ni(CN)(2)-CN-Ni(pn)(2)- in which the N(II) centers are linked by two CN groups. The formation of cyanide bridges is evident fr om the IR and W-Vis spectra by appearance of nu(CN) shifts and changes in l ambda(max) with respect to the mononuclear parent complex [Ni(CN)(4)](2-). (C) 2000 Elsevier Science S.A. All rights reserved.