title: Light-induced electron transfer in porphyrin-calixarene conjugates.
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 pi-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.
authors.affiliation: Molecular Photonics Laboratory, School of Natural Sciences Chemistry, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK. anthony.harriman@ncl.ac.uk
authors.forename: Anthony
authors.initials: A
authors.lastname: Harriman
authors.forename: Maryam
authors.initials: M
authors.lastname: Mehrabi
authors.forename: Bashkar G
authors.initials: BG
authors.lastname: Maiya
mesh_terms: D016227:Benzoquinones / Q000737:chemistry; D047250:Calixarenes / Q000737:chemistry*; D004563:Electrochemistry; D004583:Electrons; D008027:Light; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction / Q000528:radiation effects; D011166:Porphyrins / Q000737:chemistry*; D013997:Time Factors
chemical_list: D016227:Benzoquinones; D011166:Porphyrins; D047250:Calixarenes