Synthesis, Spectroscopic Properties, and Structure of [Tetrakis(2,4‐dimethyl‐3‐pentyloxy)phthalocyaninato]metal Complexes

A series of highly soluble [tetrakis(2,4‐dimethyl‐3‐pentyloxy)phthalocyaninato]metal complexes [MPc(OC7H15)4] (M = Zn, Pd, Co) were prepared by cyclic tetramerization of 3‐(2,4‐dimethyl‐3‐pentyloxy)phthalonitrile (2) in the presence of the corresponding metal salts and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in n‐pentanol. For M = Zn and Pd, two major isomers with a C4h and C2v symmetry were isolated by column chromatography and characterized with various spectroscopic methods, while the cobalt analogue showed only the C4h isomer. The (phthalocyaninato)manganese complex [MnClPc(OC7H15)4] was also synthesized by metallation of the metal‐free phthalocyanine H2Pc(OC7H15)4 formed by treating 2 with CeCl3 and DBU in n‐pentanol. The structures of the C4h isomers of the (phthalocyaninato)zinc and ‐cobalt complexes and the C4 isomer of the manganese analogue were also established by X‐ray diffraction analyses. The palladium counterpart formed a novel 1:1 inclusion complex with oxalic acid, the crystal structure of which was also determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)