Unusual self-assembled nanoaggregation of the thermally stable metal-free slipped-cofacial J-type phthalocyanine dimer

Nanoaggregation of the thermally stable bis(2-hydroxy-9(10),16(17),23(24)-tri-tert-butylphthalocyanine) of J-type was observed by the field emission scanning electron microscopy (FE-SEM). Ordered phases, represented as threads composed of about 200 nm diameter circles were discovered, unlike the parent dimeric magnesium complex, in which similar circles combine together to give visually distinguishable zones with widths of about 600 nm and the same distance between them.     

Synthesis and properties of new binuclear nickel(ii) phthalocyanines

New binuclear nickel(ii) phthalonitrile complexes, viz., Ni^II 2,2",9(10),9"(10"),17(18),17"(18"),24(25),24"(25")-tetra(phenylene-1,2-dioxy)bisphthalocyanine and Ni^II 2,2",9(10),9"(10"),17(18),17"(18"),24(25),24"(25")-tetra(4-tert-butylphenylene-1,2-dioxy)bisphthalocyanine, were synthesized. The complexes were characterized by electronic spectroscopy and MALDI—TOF mass spectrometry and studied as active components for membranes of ion-selective electrodes in solutions of dicarboxylic acids.     

Synthesis and spectroscopic properties of new boron subphthalocyanine complexes and a heteronuclear phthalocyanine complex

New boron μ-chloro-and μ-alkoxyhexabutylsubphthalocyanines were synthesized. A heteronuclear complex containing both the phthalocyanine and subphthalocyanine fragments was prepared. The spectroscopic properties of these compounds were studied. Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2020–2023, September, 2005.     

First hybrid oximehydrazonate phthalocyaninoclathrochelates: The synthesis and properties of lutetium phthalocyanine-capped cage iron(II) complexes

Ditopic oximehydrazonate iron(II) phthalocyaninoclathrochelates were synthesized by a transmetallation (a capping group exchange) reaction of the initial labile triethylantimony-capped clathrochelate iron(II) oximehydrazonates with lutetium(III) phthalocyanine as a Lewis acid. The complexes obtained were characterized using elemental analysis, PD and MALDI-TOF mass spectrometries, IR, UV–Vis, ⁵⁷Fe Mössbauer, and ¹H, ¹³C{¹H} NMR spectroscopies. An encapsulated iron(II) ion was found to be in a low-spin state. The cyclic voltammograms show oxidation and reduction waves assignable to Fe^2+/3+ couples of macrobicyclic framework and to phthalocyanine macrocycles.     

Luminescent properties of semiconductor composite systems composed of erbium triphthalocyanine molecules and a silicon slot structure in the near-infrared region

Photoluminescence spectra of organic semiconductors based on mono-, bis-, and triphthalocyanine containing erbium as a complexing agent have been obtained in the range of 1–1.8 μm. Comparison of the spectral characteristics has shown that erbium triphthalocyanine has the highest photoluminescence quantum yield at a wavelength of 1.5 μm. To enhance this effect, composite materials based on erbium triphthalocyanine and a silicon slot structure have been synthesized, in which an additional increase in the photoluminescence signal near 1.14 μm has been observed. At the same time, no photoluminescence signal has been observed near the wavelength of 1.5 μm. This can be explained by taking into account the interaction of the erbium triphthalocyanine molecules with the adsorption centers of the silicon matrix.     

Anodic Doping of Electropolymerized Copper 2,9,16,23-Tetraaminophthalocyanine

Anodic polymerization of 2,9,16,23-tetraamino substituted copper phthalocyanine is studied in 0.1 M Bu₄NBF₄and Bu₄NClO₄in dimethylformamide (DMF). The electropolymerization rate in DMF is two to three times that in dimethyl sulfoxide, due to a lesser donor ability of DMF and a weaker blocking of radical cations formed during the oxidation of initial copper phthalocyanine. According to a study of the electrochemical behavior of polymerized copper phthalocyanine in neutral aqueous solutions, the anodic doping of the polymer is accompanied by one redox transition. The two redox transitions, observed in an aqueous solution of acid, are explained by two successive steps of oxidation of an aniline-like structure or by the involvement of two protonated systems in the doping process, specifically, a stacked system (phthalocyanine ligands collected in parallel stacks) and a polyaniline system.     

Hexadecapropyloxy-substituted diphthalocyanine complexes of rare-earth elements: synthesis,spectroscopic and electrochemical studies

Hexadecapropyloxy-substituted diphthalocyanine complexes of rare-earth elements (REE = Lu, Tm, Sm) were synthesized. The new symmetrically substituted diphthalocyanine complexes prepared starting from 4,5-dipropyloxyphthalodinitrile (phthalogen) are characterized by better solubilities compared to the known hexadecamethyl-substituted diphthalocyanine complexes of the same REE. Spectral and electrochemical characteristics of the complexes were studied. The compounds can be used as materials for high-contrast electrochromic devices.     

New phthalocyanine complexes based on 4,5-isopropylidenedioxyphthalonitrile

A series of new metal monophthalocyanine complexes were synthesized from 4,5-isopropylidenedioxyphthalonitrile and their spectroscopic and electrochemical properties were studied. The removal of the protective isopropylidene groups from these compounds afforded symmetrically substituted octahydroxyphthalocyanines.