The ultraviolet absorption spectra of some chlorinated biphenyls

The UV spectra of 29 chlorobiphenyls have been examined. With increasing chloro substitution in which there are less than two chlorine groups ortho to the Ph-Ph bond the λ_max values for the κ band (attributed to conjugation between the two phenyl rings) are shifted to longer wavelengths and for the more highly substituted chlorobiphenyls there is also a bathochromic shift of the main band (due to the benzenoid skeleton). Introduction of two or more chlorine atoms ortho to the Ph-Ph bond results in a hipsochromic shift of κ band and diminished e{open} value due to steric inhibition of resonance between the two phenyl rings. The sterically hindered chlorobiphenyls and the more highly chlorinated Aroclors also exhibit a series of low-intensity finestructured absorption maxima between 268-302 nm. The UV spectra of chlorobiphenyls are particularly diagnostic with respect to the degree of substitution at the 2, 2′, 6 and 6′ positions and can be used in the structural analysis of separated chlorobiphenyls. The data may also aid in correlating the photochemical reactivities.