Symmetry lowering in crystalline solid solutions: A study of cinnamamide-thienylacrylamide by x-ray and neutron diffraction and solid-state photochemistry
Description: Principles are outlined for symmetry lowering of a mixed crystal. A survey is given of methods used to detect reduced symmetry: changes in crystal morphology, detection of enantiomeric segregation of chiral additives in centrosymmetric'' crystals, generation of second harmonic optical signals, optical birefringence, asymmetric photoreactions in the crystalline state and X-ray and neutron diffraction. The last two methods are applied to mixed crystals of cinnamamide host and thienylacrylamide. Diffraction demonstrated that the mixed crystals are composed of six sectors of reduced symmetry, from monoclinic centrosymmetric P2[sub 1]/c to triclinic P1 in four sectors and possibly Pc in the remaining two. The X-ray diffraction data were not sufficiently accurate for assigning the absolute structures of the PI sectors of anomalous X-ray scattering. Thus, by this method one could not ascertain the absolute orientation of the guest molecules on the surface sites through which they were selectively occluded. This ambiguity was resolved by assignment of the absolute configuration of the chiral heterophotodimers, between host and guest, in enantiomeric excess in the PI sectors, after irradiation with UV light. This leads to the conclusion that the selective occlusion of thienylacrylamide arises from replacement of attractive C-H[pi] (electron) interactions between host molecules by a repulsive sulfur (lone pair electron)[pi](electron) interactions between guest and host at the crystal surfaces.
Date: January 1, 1993
Creator: Shimon, L.J.W.; Weissinger-Lewin, Y.; McMullan, R.K. (Brookhaven National Lab., Upton, NY (United States)); Vaida, M.; Frolow, F.; Lahav, M. et al.
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