摘要：

The electronic structures of metal phthalocyanine polymers PcMX and MPc were examined by performing tight-binding band calculations on PcMX (MX = SiO, GeO, AlF, GaF, CrF) and MPc (M = Ni, Co, Fe) chains. The present band structure study suggests that the electrical conductivities of halogen-doped PcMX and MPc chains are governed by their valence bands a composed of the HOMO a1M of each Pc ring. It is the valence band a that becomes partially empty upon halogen-doping. The Pc ring π-orbital a1M is made up of only the carbon p orbitals. By symmetry, none of the s, p and d orbitals of a metal atom M can mix into the a1M orbital. Consequently, the width of the valence band a is solely determined by such factors as the inter-ring separation and the inter-ring rotation. It was noted that there should be one, two and three unpaired electrons on each metal atom of CoPc, FePc and PcCrF chains, respectively. Thus halogen-doped CoPc, FePc and PcCrF are expected to have magnetic properties associated with the unpaired electrons.

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