Synthesis and characterization of soluble octaaryl- and octaaryloxy-substituted metal-naphthalocyanines

An easy route for the synthesis of vanadium, zinc, magnesium, etc. complexes of new soluble symmetrical octa(m-trifluoromethylphenyl) or octa(m-trifluoromethylphenoxy) substituted 2,3-naphthalocyanines {[(m-CF3Ph)(8)NcM] or [(m-CF3PhO)(8)NcM]} in good yields is described in detail. The structures of the synthesized compounds were verified by UV/Vis and H-1 and C-13 NMR spectroscopy, as well as by mass spectrometry. The good solubilities of the prepared compounds in toluene and coordinating solvents (e.g., THF), was explained in terms of the nonplanar arrangements of eight m-CF3Ph substituents in relation to the Nc macrocycle, preventing aggregation of the molecules. The Q-bands in the UV/Vis spectra of the [(m-CF3Ph)8NcM] species are each bathochromically shifted by ca. 13 nm in relation to [(mCF(3)PhO)(8)NcM] species, appearing at 817 nm for [(m-CF3Ph)(8)NcVO] in toluene. All NcMs prepared exhibit very high molar extinction coefficients for the Q-band {1g(epsilon) approximate to 5.6} in THF. Some of prepared Nc complexes appeared to be very unstable on exposure to daylight. In addition, a nickel-catalyzed Kumada cross-coupling synthesis of substituted o-terphenyls, intermediate compounds for the preparation of octaaryl-substituted Ncs, is described. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).