Porphyrins Group 14 phthalocyanines

Bocian, Lindsey and co-workers studied sandwich complex nanocapacitors comprised of porphyrin and phthalocyanine ligands separated by lanthanide metals [133]. A triple-decker sandwich of phthalocyanine-Eu-phthalocyanine-Eu-porphy-rin, with two phenylethynyl linker wires from the porphyrin, potentially has up to nine accessible oxidation states (—4 to +4). SAMs of monomers, dimers, trimers, and oligomers of this sandwich, anchored at one or both ends by thioacetyl groups, gave charge densities up to 10 10 mol cm-2, electron-transfer rates up to 105 electrons s-1, and charge-dissipation half-lives in the 10-50 s range. 

Fig. 5.5 Scheme of n-n stacking on nanocarbons (CNT shown in example) showing (a) pyrene, (b) porphyrin, (c) phthalocyanine, (d) benzyl and (e) triphenylphosphinederivatives. M, Rand Y groups vary and can be used for further hybridization. 

Victor N. Nemykin was bom in 1968, received his M.S. in organic chemistry from Kiev State University, Kiev, Ukraine, in 1993, and his Ph.D. in inorganic chemistry from the Institute of General and Inorganic Chemistry, Kiev, Ukraine, in 1995. He was awarded a Japanese Society for the Promotion of Science Fellowship and worked in the laboratories of Professors N. Kobayashi and then K. Sakamoto at the Tohoku and Nihon Universities, Japan. He then accepted a postdoctoral position at Duquesne University in the research group of Professor P. Basu. Since fall 2004, he has been assistant professor at the Department of Chemistry and Biochemistry, University of Minnesota Duluth. He has co-authored more than 60 publications including several patents. His research interests include the chemistry of porphyrins and phthalocyanines, bioinorganic chemistry of molybdenum, and computational chemistry. 

The macrocyclic-type PCMU give mostly polymers with the corresponding groupings. Phthalocyanines [18] and porphyrins [19] are the classical examples of... 

Electrocatalytic groups such as porphyrins and phthalocyanines that act as supramolecular hosts for different metals and mimic the active sites of various proteins are commonly used in amperometric sensors [66,67]. A biomimetic sensor based on an artificial enzyme or synzyme has been demonstrated [68]. The artificial enzyme used in this study was a synthetic polymer (quaternised polyethyleneimine containing 10% primary amines) which decarboxylated oxaloacetate. The product carbon dioxide was detected potentiometrically via a gas membrane electrode. 

In order to increase the solubility of porphyrin and phthalocyanine complexes, several structural modifications have been made, a, jS, y, 6-Tetra-(4-pyridyl)-porphin complexes of copper(II), nickel(II), and zinc(II) have been synthesized (35) and their ultraviolet spectra determined in chloroform and in acid solution. By utilizing sulfonic acid groups to increase solubility, complexes of 4,4, 4",4" -tetrasulfophthalocyanine complexes of many metals were prepared (94j 95). This chelating agent was found to have a ligand field strength comparable to cyanide (94y 95). 

The macrocycle phthalocyanine contains 8 N atoms, but usually only the four N-atoms on the inner side of the cycle are able to coordinate. In fact, in most cases the synthesis of phthalocyanine is realized in the presence of a metal ion as the template. It is also possible to attach various substituents on the phthalocyanine macrocycle. As for porphyrin, when coordinating to a metal ion, the H-atoms of the two NH groups on the inner side of the phthalocyanine cycle are replaced. The incorporation of metal porphyrin and phthalocyanine complexes into porous crystals has been gaining increasing interest. The properties of the complexes located in zeolite channels or cages are usually different from those of the compounds in solution, and they may find applications in areas such as catalysis, photochemistry, electrochemistry, and biomimetics. 

Porphyrins and phthalocyanins, complexes with metalloids of groups 4A,... 

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