Journal
CHEMICAL SOCIETY REVIEWS
Volume 42, Issue 20, Pages 8122-8133Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3cs60117j
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Funding
- JSPS [23350018, 24655029, 21245011]
- Mitsubishi Chemical Corporation Fund
- Sumitomo Foundation
- Shorai Foundation for Science and Technology
- Kurata Memorial Hitachi Science and Technology Foundation
- Tokuyama Science Foundation
- Grants-in-Aid for Scientific Research [23350018, 21245011] Funding Source: KAKEN
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In chiral donor-acceptor (D-A) systems, irradiation wavelength plays vital roles in determining the photochemical consequences. Selective excitation of a D-A complex at the charge-transfer (C-T) band affords an excited C-T complex (ECT), while the local-band excitation of D or A may lead to the formation of a conventional exciplex (EX) upon subsequent interaction with the D-A partner. These two excited species, generated from the same D-A pair, may be categorized formally as excited complexes or exciplexes, but should be distinguished, provided that they significantly differ in structure and reactivity. Indeed, ECT and EX exhibit distinctly different temperature-dependent photophysical and photochemical behaviours, which are assignable to the differences in relative stability, conformational flexibility and/or solvation properties. Fine-tuning excitation wavelength further enabled us to discriminate stereoisomeric intramolecular C-T complexes through preferential excitation, as C-T complexes are generally composed of an ensemble of various geometries. Besides temperature and solvent polarity, the excitation wavelength was shown to be employed as an unconventional yet practical tool for critically controlling the chemo-, regio- and stereoselectivities in molecular and supramolecular photochemistry.
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