Synthesis, characterization, and electrochemical and electrical properties of a novel ball-type hexanuclear metallophthalo-cyanine, bridged by calix[4]arenes substituted with four hexyl-thiometallophthalocyanines through nitro coupling

Abstract

In this study, the synthesis of a supramolecular hexaphthalocyaninato hexazinc(II) with hexylthio substituents is reported. Starting from 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-dimethoxycalix[4]arene, mononitro derivative of calix[4]arene 1 was obtained. Compound 1 was converted to phthalodinitrile derivative 2 by the reaction with 4-nitrophthalonitrile in dry dimethylsulfoxide by the method of nucleophilic substitution of an activated nitro group in an aromatic ring. The tetramerization of compound 2 with Zn ( OAc )2·2 H 2 O in 1-pentanol gave the novel ball-type binuclear zinc (II) phthalocyanine 3 which was reacted with unsymmetric zinc(II) phthalocyanine 4 to furnish a supramolecular assembly of a zinc(II) phthalocyanine of a ball type with four zinc(II) phthalocyanines through azo bridges, 5. Newly synthesized compounds were characterized by elemental analysis, UV-vis, IR, MALDI-TOF MS and 1 H NMR spectra. The electrochemical and spectroelectrochemical properties of 5 were also examined in nonaqueous media. The measurements showed the formation of various mixed-valence oxidation and reduction species, due to the strong intramolecular interactions between the Pc rings. Both DC and AC conductivity data were analyzed by the existing theory.