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Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Moorthy, JN and Monahan, SL and Sunoj, RB and Chandrasekhar, J and Bohne, C (1999) Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching. In: Journal of the American Chemical Society, 121 (13). 3093-3103 .

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja9818708

Abstract

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 30 Jun 2011 10:44
Last Modified: 30 Jun 2011 10:45
URI: http://eprints.iisc.ernet.in/id/eprint/38675

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