Since the discovery of pyrene excimer formation in 1955, this phenomenon has been studied extensively and is discussed in several chapters of the classic text Photophysics of Aromatic Molecules by J.B. Birks (1970) followed by thousands of papers devoted to excimer and exciplex formation. Despite the great interest in the subject, all papers up to this date dealing with pyrene excimer formation contain an experimental flaw (an unnoticed nonhomogeneous distribution of reactants) leading to an incorrect reaction scheme. This error has caused further erroneous interpretations of the kinetics and mechanism when pyrene is used as a fluorescent probe to characterize microheterogeneous systems. Contrary to the experimental methods applied in all related previous works, the selection of a suitable excitation wavelength utilized in our study results in simple homogeneous kinetics. Consequently, the rate parameters obtained and mechanism proposed differ drastically from those published previously and are important for correct data interpretation.

Peculiarities about pyrene excimer formation mechanism and kinetics

245th National Meeting (2013)

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