Metal phthalocyanines and

The first ship-in-a-bottle type of catalyst was synthesized by Romanovsky, and Zakharov and colleagues in 19 77.54,55 Encapsulation of different metal phthalocyanines and the reactivity of these catalysts were studied by this56-63 and other research groups.64-68... 

Scheme 6 represents coordinate polymers. A low-molecular-weight compound with multidentate groups on both ends of the molecule grows into a linear polymer with metal ions, and the polymer chain is composed of coordinate bonds. The parquetlike polymer complexes, poly(metal-phthalocyanine) and poly(metal-tetracyano-ethylene), are classified into Scheme 7. They are formed by inserting metal ions into planar-network polymers or by causing a low-molecular-weight ligand derivative to react with a metal salt and a condensation reagent.

It will be shown in later sections that side groups such as aromatic azo or biphenyl units generate liquid crystallinity metal phthalocyanines and tetracyanoquino-dimethane generate electroactive domains and polyaromatic units such as naphthyl or anthracene groups alter the physical properties markedly as they attempt to align then-molecular axes or form stacks of side groups. 

Protactinium-233 and neptunium-239 diphthalocyanines are prepared from the corresponding thorium-232 and uranium-238 diphthalocyanines by element transformation [6]. The existence of Pa and Np di-Pcs is proven by repeated sublimation of the irradiated parent compounds using platinum gauze to retain the impurities. Neptunium di-Pc is also synthesized on the tracer scale from irradiated uranium metal, using the normal synthetic method for uranium di-Pc (Example 29) [6], Other actinide phthalocyanines are reported [107-114], Their structures, as well as those of 200 metal phthalocyanines and their derivatives, are classified in an excellent recent review [115]. More recent experimental data on actinide phthalocyanines are absent in the available literature. 

The importance of complexing and the polarity of the environment has been emphasized. When metal phthalocyanines and metal stearates were compared in ethyl benzoate as solvent, their catalytic efficiencies in the autoxidation of O.IM linoleic acid were of a comparable order of magnitude when the metal phthalocyanines and the metal stearates were present at concentrations of 2 X and... 

Systematic studies of the role of such factors as the nature of the metal center and the detailed structure of the chelating ring, particularly its peripheral functionalization, can afford valuable information toward unveiling structure-activity relationships for macrocycles as electrocatalysts for oxygen reduction. The following sub-sections describe some of the most salient aspects of a selected number of transition metal phthalocyanines and porphyrins, including the effects of redox and non-redox active substituents on the properties of Co porphyrins. 

Topics which have formed the subjects of reviews this year include excited state chemistry within zeolites, photoredox reactions in organic synthesis, selectivity control in one-electron reduction, the photochemistry of fullerenes, photochemical P-450 oxygenation of cyclohexene with water sensitized by dihydroxy-coordinated (tetraphenylporphyrinato)antimony(V) hexafluorophosphate, bio-mimetic radical polycyclisations of isoprenoid polyalkenes initiated by photo-induced electron transfer, photoinduced electron transfer involving C o/CjoJ comparisons between the photoinduced electron transfer reactions of 50 and aromatic carbonyl compounds, recent advances in the chemistry of pyrrolidino-fullerenes, ° photoinduced electron transfer in donor-linked fullerenes," supra-molecular model systems,and within dendrimer architecture,photoinduced electron transfer reactions of homoquinones, amines, and azo compounds, photoinduced reactions of five-membered monoheterocyclic compounds of the indigo group, photochemical and polymerisation reactions in solid Qo, photo- and redox-active [2]rotaxanes and [2]catenanes, ° reactions of sulfides and sulfenic acid derivatives with 02( Ag), photoprocesses of sulfoxides and related compounds, semiconductor photocatalysts,chemical fixation and photoreduction of carbon dioxide by metal phthalocyanines, and multiporphyrins as photosynthetic models. 

Metal phthalocyanines and porphyrins as photosensitizers for reduction of water to hydrogen. 

Mack, J. and Stillman, M.J. (2003) Electronic structure of metal phthalocyanine and porphyrin complexes from analysis of the UV-visible absorption and magnetic circular dichroism spectra and... 

Fig. 3 gives the structures of (i) six classes of good one-electron donors [TTF and friends HMTTF and friends TTT and friends BEDT-TTF perylene, and MPc (metal phthalocyanines)] and (ii) three classes of good one-electron acceptors (TCNQ, TNAP, and DCNQI). All these donors and acceptors are flat, or almost perfectly flat, molecules this requirement seems almost self-evident if one wants to form a tight crystal lattice with good intermolecular overlap. It is conceivable that this requirement could be relaxed, but a good example of this has not been found. It is known that there are small non-planarities (e.g. in BEDT-TTF) but it is not clear whether this is critical for the solid-state properties. 

Conducting Polymer Nanocomposites with Metal Phthalocyanines and Porphyrins... 

Generally, incorporating metal-phthalocyanines and porphyrins into CP matrix will decrease the conductivities of CPs [103]. However, such composites will show some enhanced chemical or physical properties such as sensing for vapors in comparison with the CPs alone which arises from their unique, specific properties such as semiconductivity, well-defined redox activity and high thermal stability [104,105]. It is well known that... 

Magdesieva, T.V., T. Yamamoto, D.A. Tryk, and A. Fujishima (2002). Electrochemical reduction of CO2 with transition metal phthalocyanine and porphyrin complexes supported on activated carbon fibers. J. Electrochem. Soc. 149(6), D89-D95. Atoguchi, T., A. Aramata, A. Kazusaka, and M. Enyo (1991). Cobalt (II)-tetraphenylporphyrin-pyridine complex fixed on a glassy carbon electrode and its prominent catalytic activity for reduction of carbon dioxide. J. Chem. Soc. Chem. Commun. 13, 156-157. 

Magdesieva, T.V., T. Yamamoto, D.A. Tryk, and A. Fujishima (2002). Electrochemical reduction of CO2 with transition metal phthalocyanine and porphyrin complexes supported on activated carbon fibers. J. Electrochem. Soc. 149(6), D89-D95. 

Darwent, J.R., P. Douglas, A. Harriman, G. Porter, and M.-C. Richoux (1982). Metal phthalocyanines and porphyrins as photosensitizers for reduction of water to hydrogen. Coord. Chem. Rev. 44, 83-126. 

Beck F, Dammert W, Heiss J, Hiller H, Polster R (1973) Electrocatalysis of the oxygen cathode by metal-phthalocyanines and -dibenzotetraazaannulenes. Z Naturforsch Teil A 28 1009-1021... 

Reductive Dehalogenations Microemulsions are usually more useful than micelles for electrochemical synthetic applications because larger amounts of polar and nonpolar reactants can be solubilized. Electrochemical catalysis has been used in microemulsions for the electrolytic conversion of organohalide pollutants to hydrocarbons [53] using mediators such as metal phthalocyanines and cobalt complexes. Microemulsions were used for the complete electrochemical catalytic... 

Kruusenberg I, Matisen L, Tammeveski K. Oxygen electroreduction on multi-walled carbon nanotube supported metal phthalocyanines and porphyrins in acid media. Int J Electrochem Sci 2013 8 1057-66. 

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