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(OC 7 H 15 ) 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 C 4 h and C 2 v symmetry were isolated by column chromatography and characterized with various spectroscopic methods, while the cobalt analogue showed only the C 4 h isomer. The (phthalocyaninato)manganese complex [MnClPc(OC 7 H 15 ) 4 ] was also synthesized by metallation of the metal‐free phthalocyanine H 2 Pc(OC 7 H 15 ) 4 formed by treating 2 with CeCl 3 and DBU in n ‐pentanol. The structures of the C 4 h isomers of the (phthalocyaninato)zinc and ‐cobalt complexes and the C 4 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)