Abstract
Simulated absorbance data have been used to demonstrate the effects of 2:1 molecular complexes on formation constants and absorptivities calculated for 1:1 donor–acceptor interactions. By systematic variation of associated spectral, thermodynamic, and concentration parameters for these systems, it is found that previous attempts to describe effects produced by the presence of more than one stoichiometric complex species are inadequate. Formation constants and absorptivities calculated with the assumption of a simple 1:1 interaction may be increased or decreased by the occurrence of higher order complexes. These variations depend largely on the ratios of complex absorptivities, relative formation constants, and the range of donor concentrations. Equations incorporating 5 of the experimental variables permit the prediction of formation constants and absorptivities to a high degree of accuracy.
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