Journal
CHEMICAL PHYSICS LETTERS
Volume 323, Issue 3-4, Pages 351-360Publisher
ELSEVIER
DOI: 10.1016/S0009-2614(00)00473-5
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Dual fluorescence and fast intramolecular charge transfer (ICT) is observed with 4-(diisopropylamino)benzonitrile (DIABN) in alkane solvents. The rate constant k(a) for the reaction from the locally excited (LE) to the ICT state has a value of 3.4 x 10(11) s(-1) in n-hexane at 25 degrees C, with an activation energy E-a of 6 kT mol(-1). Efficient intersystem crossing with a yield of 0.94 takes place from the ICT state. With 4-(dimethylamino)benzonitrile, in contrast, dual fluorescence is not observed in alkanes. The charge transfer reaction of DIABN is mainly favoured by its small energy gap Delta E(S-1,S-2), in accordance with the PICT model for ICT in aminobenzonitriles. (C) 2000 Elsevier Science B.V. All rights reserved.
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