Study of the catalytic activity of electrochemically reduced forms of phthalocyanines in the reaction of CO2 with epoxides

Catalytic activity of electrochemically reduced forms of mono- and diphthalocyanine complexes of transition and rare-earth elements in the reaction of carbon dioxide with epoxides is considerably higher than that of corresponding neutral forms. The catalytic efficiency depends on the nature of the phthalocyanine complex, the method of the catalyst immobilization, and the electrophilicity of epoxide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2205–2213, November, 1998.     

The development of highly selective approaches to sandwich-type heteroleptic double- and triple-decker lutetium(III) and europium(III) phthalocyanine complexes

The selective synthesis of heteroleptic (heteronuclear) sandwich-type lanthanide phthalocyanines has been accomplished. Double-decker complexes ^BuPcLnPc, and ^BuPcLnPc^Cl (Ln = Lu, Eu; ^BuPc = 2,3,9,10,16,17,23,24-octabutylphthalocyaninate; Pc = phthalocyaninate, ^ClPc = 2,3,9,10,16,17,23,24-octachlorophthalocyaninate) were obtained in good yields by a direct interaction of metal-free ligand ^BuPcH₂ with the monophthalocyanines PcLnOAc or ^ClPcLnOAc. Heteronuclear triple-decker phthalocyanines PcEu^RPcLu^RPc, ^ClPcEu^RPcLu^RPc and ^BuPcEu^RPcLu^RPc (^RPc = ^BuPc, ^tBuPc; ^tBuPc = 2(3),9(10),16(17),23(24)-tetra-tert-butylphthalocyaninate) were obtained from the corresponding mono-(PcEuOAc, ^ClPcEuOAc, ^BuPcEuOAc) and bisphthalocyanines (^RPc₂Lu) under similar conditions.     

Synthesis and spectroscopic properties of new water-soluble phthalocyanines containing pyridinium hydrochloride fragments

New 2,9,16,23-tetra[o-(hydroxymethyl)benzyloxy]-substituted phthalocyanines were synthesized. Their reaction with 4-bromopyridine afforded 2,9,16,23-tetra[o-(4-pyridyloxymethyl)benzyloxy]-substituted analogs, treatment of which with HCl led to water-soluble pyridinium salts. Spectroscopic properties of the phthalocyanines obtained were studied and a hypsochromic shift of the Q-band of the hydrochloride as compared with the corresponding pyridinium analogs was observed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 2007.     

Correlations between electrochemical and spectral properties of alkyl-substituted diphthalocyanine lanthanide complexes

The electrochemical behavior and spectral properties of a series of symmetrical 2,3,9,10,16,17,23,24,2’,3’,9’, 10’,16’,17’,23’,24’-hexadecaalkyl-substituted lanthanide complexes (R₈Pc)₂Ln (R = H, Me, Et, Buⁿ; Ln = Eu, Dy, Lu) were studied. Regularities of changing the parameters under study were established, depending on the nature of lanthanide and substituents in the phthalocyanine macroligands. The position of the intervalence band of the complexes in the near-IR region depends on the effective distance between the macroligands and also on the electronic effect of the substituents. Correlations between the electrochemical and spectral properties of the complexes were found.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 184–189, January, 2005.     

Synthesis of new lanthanide naphthalocyanine complexes based on 6,7-bis(phenoxy)-2,3-naphthalodinitrile and their spectral and electrochemical investigation

A number of naphthalocyanine and dinaphthalocyanine complexes of the rare-earth elements based on 6,7-bis(phenoxy)-2,3-naphthalodinitrile obtained for the first time has been synthesized and their spectral properties have been investigated. Electrochemical behavior of lutetium [bis(octaphenoxy)naphthalocyanine] in the thin hydrophobic films has been studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1885, September, 2008.     

Cobalt(II) porphyrazine as an active component of iodide-selective electrodes

Cobalt(II) porphyrazine is synthesized and studied as an active component of a polyvinyl chloride plasticized membrane ion-selective electrodes (ISEs). It is established that regardless of their structure, ISEs are sensitive to iodide. The introduction to the ISE of an ionic additive, ionic liquid 1,3-dihexadecylimidazolium chloride, significantly improves the electrochemical characteristics: the slope of the electrode function reaches ?(57 ± 1) mV/dec, c_min = 8.3 × 10^–6 M. Solid-state screen-printed electrodes the surfaces of which are modified by a 1: 4 mixture of cobalt(II) porphyrazine and ionic liquid 1,3-dihexadecylimidazolium chloride demonstrate satisfactory electrochemical characteristics: the slope of the electrode function is ?(56 ± 4) mV/dec and c_min = 2.5 × 10^–5 M. The potentiometric selectivity of the ISEs for iodide is studied. It is found that the effect of lipophilic interfering ions is significantly lower for solid state ISEs than for plasticized membrane electrodes.     

A New Approach to Calculation of Secular Frequencies in the Dynamics of Near-Earth Objects in Orbits with Large Eccentricities

Russian Physics Journal - A modified method for identifying and studying secular resonances in the dynamics of near-Earth objects is described. Unlike the traditionally used approach based on...     

Metal phthalocyanine-catalyzed addition of polychlorine-containing organic compounds to C=C bonds

Russian Chemical Bulletin - Organopolychlorine compounds (CCl4, CCl3CO2Et, CCl3CHO) add at the double bond of various olefins under the catalysis of the metal phthalocyanine complexes. A...     

Synthesis and spectral and electrochemical properties of hexadecamethyl-substituted diphthalocyanines of rare-earth metals

A new method for the preparation of 3,5-dimethyl-o-phthalodinitrile was proposed, and the substituted diphthalocyanine complexes of Lu^III, Tm^III, Er^III, and Dy^III were synthesized. The spectral and electrochemical characteristics of the complexes were found. The complexes can be used as materials for electrochromic devices with high contrast.