Band Structures of 1D (Porphyrinato)Ni(II) Systems

In the model calculations reviewed in the last section we have discussed possible interrelations between the stacking geometry of organometallic 1D chains (i.e. intercell separation), on one side, and electronic structure effects (i.e. torsional barriers, magnitude of intra- and intercell energies, charge distribution, etc.), on the other. One-dimensional (porphyrinato)NI(II) systems are suitable materials to quantify correlations between structural parameters and physical or chemical solid-state properties. In fig. IV.21 we have displayed four (prophyrinato)Ni(II), Ni(p), systems that have been the subject of a number of experimental [IV.35,IV.83–1V.85] and theoretical [IV.36,IV.86–IV.89] studies. These 1D solids show significant changes in the nature of injected carriers, paramagnetic susceptibi1ities χP and the temperature dependence of the electric conductivity σ as response to structural changes in the macrocyclic π ligand.