Synthesis, characterisation and structural investigations of iodine-doped indium(III) and zirconium(IV) diphthalocyanines: [InPc2]I2 and [ZrPc2]I2

摘要: Abstract Crystals of iodine-doped indium(III) and zirconium(IV) diphthalocyanines, [InPc2]I2 [ZrPc2]I2, were grown directly in the reaction In–Tl alloy or zirconium powder with 1,2-dicyanobenzene under a stream iodine at about 200 °C. Both partially oxidised diphthalocyaninato complexes crystallise P4/mcc space group tetragonal system one molecule per unit cell. The requires that central metal ions are disordered these structures. crystal structures shown columnar pseudo-one-dimensional stacks [InPc2] [ZrPc2] units non-integral charge linear chains symmetrical triiodide I3 − ions, which detected by Raman spectroscopy. aggregates [InPc2]2/3+ [ZrPc2]2/3+ as well aligned along [001] direction. formal oxidation state Pc macrorings equals to ≅−1.167 ≅−1.667 complexes. EPR measurement shows single sharp line g=2.0028 2.0026 for indium complexes, respectively. conductivity on polycrystalline samples room temperature 2.7–3.1×10−2 5.2–5.5×10−2 Ω−1 cm−1 transport proceeds mainly [MPc2]2/3+ aggregates. metallodiphthalocyaninato exhibit non-metallic character (dσ/dT>0).