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Interaction between intramolecular charge transfer state of p-N,N-dimethylaminobenzonitrile and amines. Stereo-controlled fluorescence quenching

1985; Elsevier BV; Volume: 116; Issue: 4 Linguagem: Inglês

10.1016/0009-2614(85)80170-6

1873-4448

Ying Wang,

Photochemistry and Electron Transfer Studies

The first excited singlet state, an intramolecular charge transfer state, of p-N,N-dimethylaminobenzonitrile (DMABN) is quenched by tertiary amines. The quenching rate cannot be correlated with the oxidation potential of the amines, but is controlled by the size of the amine alkyl group. This unusual steric effect indicates a short-range interaction, which we attribute to three-electron bonding. Excited-state three-electron bonding interaction should be a general phenomenon and can lead to the formation of sigma-bonded exciplexes. The implication of this result on the origin of the anomalous dual fluorescence of DMABN is discussed.