title: Synthesis, isolation, and structural characterization of the C4h isomer of metal(1,2-naphthalocyanine) and its one-dimensional conductor of the axially substituted species.
abstract: The C4h isomer of the 1,2-Nc (1,2-naphthalocyaninato) ligand has been efficiently isolated as a hydrated magnesium complex by the fractional crystallization from the benzene/acetone solution after treating the crude mixture of the four isomers (C4h, C(s), C2v, D2h) with benzene. The C4h symmetry has been confirmed by X-ray structure analysis. The central metal ion has been demetalated and subsequently converted to the Li2 complex followed by conversion to the cobalt(II) complex. Electrochemical oxidation of the Co(III)(1,2-Nc)(CN)2 anion prepared from the cobalt(II) complex with TPP (tetraphenylphosphonium) has yielded a partially oxidized salt, TPP[Co(III)(1,2-Nc-C4h(CN)2]2. The crystal comprises slipped stacked Co(III)(1,2-Nc-C4h)(CN)2 one-dimensional chains and one-dimensional arrays of TPPs. The conductivity at room temperature is 0.1 S cm(-1), and the temperature dependence is semiconducting with a small activation energy of about 0.05 eV. The positive temperature-independent value of about 60 microV deg(-1) observed in the thermoelectric power measurements suggests that the salt is in the correlated hopping regime.
authors: Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
authors: Eduardo H
authors: EH
authors: Gacho
authors: Hiroyuki
authors: H
authors: Imai
authors: Ryo
authors: R
authors: Tsunashima
authors: Toshio
authors: T
authors: Naito
authors: Tamotsu
authors: T
authors: Inabe
authors: Nagao
authors: N
authors: Kobayashi