Nearly separable isomerizing systems

Ke, the intramolecular excimer equilibrium constant under conditions where the dynamics or rotational Isomeric transitions is suppressed, is examined on the basis of the theory of macrocyclization [Flory, P. J.-, Suter, U. W. Mutter, M. J. Am. Chem. Soc. 1976, 98, 5733, 5740,5745], The conformational averages of the required moments and polynomials are calculated using their exact matrix generation method. The calculations can rationalize the appearance of a maximum near m = 15 In the 1 1 M that have been reported for pyrene-(CH2lrn-pyrene. In order to achieve this agreement, It is Imperative that the theoretical analysis incorporate the probability of a proper angular correlation of the two pyrene ring systems when the separation of their centers Is 0.35 nm. 

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