Electronic Spectroscopy of Highly-Polar Aromatics. VI. A Self-Complex of N,N-Dialkyl-p-Cyanoanilines

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Abstract
The absorption and luminescence spectra of N,N-dialkyl-p-cyanoanilines are reported. A weak absorption band at ∼ 29000cm−1 is assigned to a self-complex of these molecules. Assuming a dimeric form for the self-complex, the association constant is 50 ≤ K ≤ 150 l/m. Excitation in the self-complex absorption region produces a phosphorescence and fluorescence which are at lower energies than the corresponding monomer luminescences; the new emissions are assigned to T1 D ← 1S0 D and 1S1 D ←1S0 D events in the self-complex. The energies of, and transition probabilities in the self-complex are rationalized using a dimer stoichiometry and a model based on dipole-dipole interactions of static and transition moment type.