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Light-induced electron transfer in porphyrin–calixarene conjugates

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Abstract

The fluorescence from a set of porphyrin–calixarene complexes is quenched upon addition of benzo-1,4-quinone (BQ) in fluid solution. In N,N-dimethylformamide solution, fluorescence quenching involves both static and dynamic interactions but there are no obvious differences between porphyrins with or without the appended calixarene. Under such conditions, the static quenching behaviour is attributed to π-complexation between the reactants and it is concluded that the calixarene cavity does not bind BQ. An additional static component is apparent in dichloromethane solution. This latter effect involves partial fluorescence quenching, for which the intramolecular rate constant can be obtained by time-resolved fluorescence spectroscopy. The derived rate constants depend on molecular structure in a manner consistent with fluorescence quenching being due to electron transfer. In all cases, however, the dominant quenching step involves diffusional contact between the porphyrin nucleus and a non-bound molecule of BQ.

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Authors and Affiliations

  1. Molecular Photonics Laboratory, School of Natural Sciences Chemistry, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK, NE1 7RU

    Anthony Harriman & Maryam Mehrabi

  2. School of Chemistry, University of Hyderabad, Hyderabad, India, 500 046

    Bashkar G. Maiya

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  1. Anthony Harriman
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  2. Maryam Mehrabi
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Correspondence to Anthony Harriman.

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Dedicated to Professor Hiroshi Masuhara on the occasion of his 60th birthday.

Deceased 21st March 2004.

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Harriman, A., Mehrabi, M. & Maiya, B.G. Light-induced electron transfer in porphyrin–calixarene conjugates. Photochem Photobiol Sci 4, 47–53 (2005). https://doi.org/10.1039/b410141c

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