Nonplanarity and its implications on triplet state characteristics of basket handle porphyrins

Ravikanth, M. ; Reddy, Damodar ; Chandrashekar, T. K. (1994) Nonplanarity and its implications on triplet state characteristics of basket handle porphyrins Chemical Physics Letters, 222 (6). pp. 563-570. ISSN 0009-2614

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Official URL: http://www.sciencedirect.com/science/article/pii/0...

Related URL: http://dx.doi.org/10.1016/0009-2614(94)00403-X

Abstract

The influence of non-planarity in the porphyrin ring on the triplet state characteristics of free base and Zn(II) derivatives of basket handle porphyrins is investigated by triplet ESR. The deviation of the zero-field splitting parameter, D, from planar H2TPP or ZnTPP is dependent on the degree of non-planarity and increases as the non-planarity increases. The electron spin polarization (ESP) pattern for most derivatives remains the same as observed for H2TPP or ZnTPP. However, MSICI8, PSIBr8, ZnMSIICI8 and Znbutyl II show different ESP patterns, suggesting a redirection of the spin sublevel activity in these isomers. The ESP pattern for PSIBr8 is temperature dependent (eeaeaa at −160°C and eeeaaa at −106°C). The calculated structure using molecular mechanics reveals maximum deformation in these isomers which in turn governs the population and decay of the triplet sublevels. The structures indicate a different orientation of bridging phenyl groups in PSIBr8 and MSICl8 with respect to the porphyrin plane.

Item Type:Article
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ID Code:104498
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