Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 130, Issue 43, Pages 14263-14272Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja804665y
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Funding
- National Science Foundation [CHE 0804015]
- Ministry of Education, Culture, Sports, Science and Technology, Japan [19205019, 19750034]
- Polish Ministry of Research and Higher Education
- Grants-in-Aid for Scientific Research [19750034] Funding Source: KAKEN
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [804015] Funding Source: National Science Foundation
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The first example of covalently linked free-base corrole-fullerene dyads is reported. In the newly synthesized dyads, the free-energy calculations performed by employing the redox and singlet excited-state energy in both polar and nonpolar solvents suggested the possibility of electron transfer from the excited singlet state of corrole to the fullerene entity. Accordingly, steady-state and time-resolved emission studies revealed efficient fluorescence quenching of the corrole entity in the dyads. Further studies involving femtosecond laser flash photolysis and nanosecond transient absorption studies confirmed electron transfer to be the quenching mechanism, in which the electron-transfer product, the fullerene anion radical, was able to be spectrally characterized. The rate of charge separation, k(CS), was found to be on the order of 10(10)-10(11) s(-1), suggesting an efficient photoinduced electron-transfer process. Interestingly, the rate of charge recombination, k(CR), was slower by 5 orders of magnitude in nonpolar solvents, cyclohexane and toluene, resulting in a radical ion-pair lasting for several microseconds. Careful analysis of the kinetic and thermodynamic data using the Marcus approach revealed that this novel feature is due to appropriately positioning the energy level of the charge-separated state below the triplet states of either of the donor and acceptor entities in both polar and nonpolar solvents, a feature that was not evident in donor-acceptor dyads constructed using symmetric tetrapyrroles as electron donors.
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