Nonplanar porphyrinates

Nonplanar porphyrins and their significance in proteins 98CSR31. 

Ravikanth M, Chandrashekar TK (1995) Nonplanar Porphyrins and Their Biological Relevance Ground and Excited State Dynamics. 82 105-188 Rawle SC, see Cooper SR (1990) 72 1-72 Raymond KN, see Baker EC (1976) 25 21-66... 

A detailed analysis of Ni11 complexes with mew-substituted porphyrins bearing zero, one, two, or four /-butyl groups revealed that both the out-of-plane and in-plane distortion depend on the perturbation symmetry of the peripheral substituents (number and position of substitutents), and their orientation.1775 These results have implications for understanding the role of nonplanar distortions in the function of metalloproteins containing nonplanar porphyrins.1776... 

The functionalization of zinc porphyrin complexes has been studied with respect to the variation in properties. The structure and photophysics of octafluorotetraphenylporphyrin zinc complexes were studied.762 Octabromoporphyrin zinc complexes have been synthesized and the effects on the 11 NMR and redox potential of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin were observed.763 The chiral nonplanar porphyrin zinc 3,7,8,12,13,17,18-heptabromo-2-(2-methoxyphenyl)-5,10,15,20-tetraphenylporphyrin was synthesized and characterized.764 X-ray structures for cation radical zinc 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin and the iodinated product that results from reaction with iodine and silver(I) have been reported.765 Molecular mechanics calculations, X-ray structures, and resonance Raman spectroscopy compared the distortion due to zinc and other metal incorporation into meso dialkyl-substituted porphyrins. Zinc disfavors ruffling over doming with the total amount of nonplanar distortion reduced relative to smaller metals.766 Resonance Raman spectroscopy has also been used to study the lowest-energy triplet state of zinc tetraphenylporphyrin.767... 

The last category was concerned with miscellaneous subjects, while citing some chirogenic porphyrin-based systems. Representative reviews include chiral lanthanide complexes by Aspinall [41], coordination chemistry of tin porphyrins by Arnold and Blok [42], photoprocesses of copper complexes that bind to DNA by McMillin and McNett [43], nonplanar porphyrins and their significance in proteins by Shelnutt et al. [44], cytochrome P450 biomimetic systems by Feiters, Rowan, and Nolte [45] and phthalocyanines by Kobayashi [46,47]. 

Nonplanar Porphyrins and Their Biological Relevance Ground and Excited State Dynamics... 

The aim of the present article is to understand nature s preference for nonplanar porphyrin systems at the active site of several biomolecules. Schiedt and Lee in their article on Recent Advances in the Stereochemistry of Metal-lotetrapyrroles have attempted some structure-function correlations based on the crystal structure analysis [10]. However, the present article is not an extension of it. Here, we have mainly concentrated on the need for the nonplanar conformations of porphyrins in biosystems and critically analysed the... 

Nonplanar porphyrin cores are found in several biomolecules and brief description of these is outlined below. 

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