In this study, the preparation of some novel metallophthalocyanine (MPcs) complexes substituted with octakis(mercaptopropylisobutyl-POSS) functional group was achieved. By the reaction of [1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane 1 with 4,5-dichloro-1,2-dicyanobenzene 2 in THF as the solvent in the presence of K2CO3 as the base, the phthalonitrile derivative 3 was synthesized. Compound 3 reacted with CoCl2 x 6H2O in ethylene glycol to furnish a novel cobalt(II) phthalocyanine . The tetramerization of 3 with urea and CuCl in the absence of solvent gave the novel Cu(II) phthalocyanine 4; while with Zn(OAc)2 x 2H2O in dry DMF gave the novel zinc(ii) phthalocyanine 6. The structures of the target compounds were confirmed by elemental analysis, UV/VIS, IR, MALDI-TOF MS and 1H NMR spectra. Nonlinear absorptions of MPcs in chloroform solution were investigated by using Z-scan measurement technique with 4 ns pulses at 532 nm wavelength. While CuPc 5 showed very high nonlinear absorption, MPcs 4 and 6 did not show considerable nonlinear absorption. Investigations of optical limiting properties of 5 revealed that this material is a very good candidate for optical limiting applications.
The novel ball-type four cyclopentyldisilanoxy-POSS bridged binuclear metallophthalocyanines 4-6 (M = Zn, Co, Cu) were synthesized from the corresponding phthalodinitrile derivative 3 which can be obtained from the reaction of cyclopentyldisilanol-POSS 1 with 4-nitrophthalonitrile 2 in THF in the presence of K(2)CO(3) as the base by nucleophilic substitution of an activated nitro group in an aromatic ring. The structures of the target compounds have been characterized by elemental analysis, UV-Vis, IR, MALDI-TOF mass and (1)H-NMR spectroscopy techniques. The catalytic activity of the 5-based catalyst towards oxygen reduction in a fuel cell-similar medium involving carbon support and Nafion was observed to be superior when compared to those of 4-and 6-based catalysts, suggesting clearly that the presence of two cofacial redox-active metal centres in the ball-type structure increases the oxygen binding capability of the metal centre and the tendency for the formation of mu-peroxo species. The effect of heat treatment on the dc electrical conductivity and the impedance spectra of the films of 4 and 5 were also studied. The results showed that there were no considerable effects of heat treatment on the dc conductivity of the film of 4. On the other hand, after the films of 5 were annealed at 448 K in vacuum, the conductivity of the films increased approximately 10(3) times.
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