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Inter And Intramolecular Interactions Of Porphyrins With 5,5′-Dithiobis(2-Nitrobenzoic Acid)

D'Souza, Francis and Krishnan, V (1992) Inter And Intramolecular Interactions Of Porphyrins With 5,5′-Dithiobis(2-Nitrobenzoic Acid). In: Photochemistry and Photobiology, 56 (2). pp. 145-156.

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Official URL: http://onlinelibrary.wiley.com/doi/10.1111/j.1751-...


meso-Tetraphenylporphyrin and its metal [zinc(II) and copper(II)] derivatives form both inter and intramolecular complexes with 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB). The nature of interaction is predominantly charge transfer (CT) in origin, with the porphyrin functioning as a II-donor and DTNB as an acceptor. Among the covalently linked intramolecular systems, the magnitude of CT interaction varies with the position (of one of the aryl groups of the porphyrin) to which DTNB is attached as ortho meta > para. Steady-state and time-resolved fluorescence studies revealed electron transfer to be the dominant pathway for the fluorescence quenching in these systems. Steady-state photolysis experiments probed using EPR and optical absorption studies have shown that electron transfer (from the excited singlet state of the porphyrin) to DTNB results in the formation of thiyl radical and production of free thiolate anion. It is found that the products of electrochemical reduction of covalently linked porphyrin-DTNB systems are different from those observed for the photochemical studies.

Item Type: Journal Article
Publication: Photochemistry and Photobiology
Publisher: John Wiley and Sons
Additional Information: Copyright of this article belongs to John Wiley and Sons.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 05 May 2011 07:26
Last Modified: 05 May 2011 07:26
URI: http://eprints.iisc.ac.in/id/eprint/37059

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