The Band Structure of the One-Dimensional (Bisglyoximato)Ni(II) System
(Bisglyoximato)Ni(II), Ni(gly)2 see fig. IV.16, is employed for an analysis of torsional energies in 1D organometallic systems as well as a quantification of intracell and intercell interactions as a function of certain details of the stacking geometry. Ni(gly)2 has been the subject of tight-binding studies on the basis of the semiempirical INDO CO Hamiltonian that has been used as principal computational framework for the present lecture note [IV.74–1V.77]; a simple one-electron approach based on the popular Wolfsberg-Helmholtz Hamiltonian has been published at the same time [IV.78]. Ni(gly)2 and a large number of alkyl or phenyl derivatives belong to a class of organometallic 1D systems that have been studied extensively in the late seventies [IV.79,IV.80]. Experimental studies have shown that partial oxidation with Br or I leads to conductivities and transport properties that are characteristic for semiconducting solids. The relevant experimental quantities are neither a function of the transition-metal center (Ni or Pd) nor a function of the halide sites (Br or I). The predominant halide component in Ni(gly)I is I 5 − ; the fractional oxidation state in the 1D column is thus +0.2.
KeywordsUnit Cell Dimension Rotational Barrier Torsional Energy Stagger Conformation Organometallic System
Unable to display preview. Download preview PDF.