Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 110, Issue 26, Pages 7994-8002Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp054992c
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Funding
- Engineering and Physical Sciences Research Council [EP/C007727/1] Funding Source: researchfish
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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.
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