ABSTRACT
The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X-ray diffraction reveal a complex lamellar structure of benzamide form II needle-like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non-classical morphologies.
ABSTRACT
Symmetry considerations preclude the possibility of twist or continuous helical symmetry in bulk crystalline structures. However, as has been shown nearly a century ago, twisted molecular crystals are ubiquitous and can be formed by about 1/4 of organic substances. Despite its ubiquity, this phenomenon has so far not been satisfactorily explained. In this work we study twisted molecular crystals as geometrically frustrated assemblies. We model the molecular constituents as uniaxially twisted cubes and examine their crystalline assembly. We exploit a renormalization group (RG) approach to follow the growth of the rod-like twisted crystals these constituents produce, inquiring in every step into the evolution of their morphology, response functions and residual energy. The gradual untwisting of the rod-like frustrated crystals predicted by the RG approach is verified experimentally using silicone rubber models of similar geometry. Our theory provides a mechanism for the conveyance of twist across length-scales observed experimentally and reconciles the apparent paradox of a twisted single crystal as a finite size effect.
