Synthese von Bis[pyridin-phthalocyaninato(1,5-)iridium(II)]iodid und Pyridin-iodo-phthalocyaninato(2-)iridium(III)-Pyridin durch schrittweise Oxydation von Bis[pyridin-phthalocyaninato(2-)iridium(II)]/Synthesis of Bis[pyridine-phthalocyaninato(1,5-)iridium(II)] Iodide and Pyridine-iodo-phthalocyaninato(2-)iridium(III)-Pyridine by Successive Oxidation of Bis[pyridine-phthalocyaninato(2-)iridium(II)

Abstract

Abstract Successive oxidation of bis[pyridine-phthalocyaninato(2-)iridium(II)] with iodine first yields mixed-valent bis[pyridine-phthalocyaninato(1,5-)iridium(II)] iodide ([(Ir(py)pc1.5-}2]I) and then pyridine-iodo-phthalocyaninato(2-)iridium(III)-pyridine ([Ir(py)(I)pc2-]·py). The latter crystallizes monoclinically with the following cell parameters: a = 10.258(1) Å, b = 17.589(3) Å, c = 19.723(2) Å, β = 92.95(1)°, space group P21/n, Z = 4. IrIII is in the centre of a slightly distorted pc2- ligand and coordinates pyridine and iodide in a trans-arrangement. The average Ir-Niso distance is 1.995(5) Å (Niso: isoindole N atom), the Ir-Npy and Ir-I distan­ces are 2.102(5) and 2.657(1)Å, respectively. By a similar oxidation of [{Rh(py)pc2- }2] only [Rh(py)(I)pc2- ]·py is obtained. Solid state spectral properties with diagnostic absorption bands at 1360. 1456, 5620 and 19800 cm-1 confirm the mixed-valent diphthalocyaninate(1.5-).