The effect of nitrile geometry (linear vs. bent) on the singlet-state properties of benzonitrile and p-dimethylaminobenzonitrile has been investigated by means of INDO/S calculations. A low-energy bent singlet state of benzonitrile has been identified and apparently is the hidden state previously detected by Huang and Lombardi. The role of this state in the photochemical cycloaddition reactions of benzonitrile is discussed. A low-energy bent state has also been identified for p-dimethylaminobenzonitrile; however, it does not appear to be either of the two fluorescent states observed for this molecule.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry