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Electron transfer in self-assembled orthogonal structures

Lookup NU author(s): Emeritus Professor Anthony Harriman, James Rostron


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Two new molecular dyads, comprising pyrromethene (bodipy) and 2,2′:6′,2″-terpyridine (terpy) subunits, have been synthesized and fully characterized. Absorption and fluorescence spectral profiles are dominated by contributions from the bodipy unit. Zinc(II) cations bind to the vacant terpy ligand to form both 1:1 and 1:2 (cation:ligand) complexes, as evidenced by X-ray structural data, NMR and spectrophotometric titrations. Attachment of the cations is accompanied by a substantial decrease in fluorescence from the bodipy chromophore due to intramolecular electron transfer across the orthogonal structure. At low temperature, nuclear tunneling occurs and the rate of electron transfer is essentially activationless. However, activated electron transfer is seen at higher temperatures and allows calculation of the corresponding reorganization energy and electronic coupling matrix element. In both cases, charge recombination is faster than charge separation. © 2006 American Chemical Society.

Publication metadata

Author(s): Harriman A, Rostron JP, Cesario M, Ulrich G, Ziessel R

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry A

Year: 2006

Volume: 110

Issue: 26

Pages: 7994-8002

ISSN (print): 1089-5639

ISSN (electronic): 1520-5215

Publisher: American Chemical Society


DOI: 10.1021/jp054992c

PubMed id: 16805483


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