Dahal, S and Krishnan, V and Nethaji, M (1998) Isomers of beta-substituted di and tri-nitrotetraphenylporphyrins and their copper(II) derivatives: Structure, optical and electrochemical redox properties. In: Proceddings of The Indian Academy of Sceinces Chemical Sciences, 110 (01). pp. 37-52.
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Abstract
Controlled nitration of meso-tetraphenylporphyrinato copper(II) using fuming nitric acid leads to the formation of different beta-substituted nitro derivatives. Five isomers of dinitro and three isomers of trinitrotetraphenylporphyrins have been isolated and characterised using FAB/MS, H-1 NMR, UV-VIS and IR spectroscopies. The single crystal X-ray data on the copper(II) derivative of one of the isomers of trinitrotetraphenylporphyrin revealed 'saddle' conformation of the porphyrin core resulting from the nitro group substitution at the beta-pyrrole carbons. The electrochemical redox behaviour of the free-base porphyrins and their copper(II) derivatives revealed that successive substitution of nitro groups at the pyrrole carbons shifts the one-electron ring oxidations anodically while the ring reduction occurs at a less cathodic potential relative to the unsubstituted porphyrin. The isomer specific shifts in the redox potentials bear a direct relationship with the relative energy levels of HOMO/LUMO obtained from AM1 calculations.
Item Type: | Journal Article |
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Publication: | Proceddings of The Indian Academy of Sceinces Chemical Sciences |
Publisher: | Indian Academy Of Sciences |
Additional Information: | Copyright of this article belongs to Indian Academy Of Sciences. |
Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
Date Deposited: | 22 Dec 2009 09:33 |
Last Modified: | 19 Sep 2010 05:25 |
URI: | http://eprints.iisc.ac.in/id/eprint/18798 |
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