PubMed2002
Urea inclusion compounds (UICs) have been used as tools to understand ferroelastic domain switching and molecular recognition during crystal growth. Although the vast majority of UICs contain helical arrangements of host H-bonds, those containing guests with the formula X(CH(2))(6)Y (X, Y = Br, Cl, CN, NC) adopt an alternative P2(1)/n packing mode in which the host molecules exist as stacked loops of urea hexamers. Such structures may be further separated into two classes, ones distorted away from hexagonal symmetry along [100] (Br(CH(2))(6)Br, Br(CH(2))(6)Cl, and Cl(CH(2))(6)Cl) and those distorted along [001] (e.g. NC(CH(2))(6)CN). In each of these systems, guests exist as equilibrium mixtures of gauche conformers whose populations control the direction and magnitude of the observed distortion. Such UICs are potentially ferroelastic, but the n-glide requires that domains are not related by a simple rotation-translation mechanism as in the helical systems. Ferroelastic (degenerate) domain reorientation would necessitate a large-scale reorganization of the urea framework and rupture of numerous H-bonds. Coupled with distortions of 2 to 10%, this mechanism-based barrier to domain switching has precluded observation of this phenomenon. To prepare ferroelastic UICs with minimal distortions from hexagonal symmetry, attempts were made to form solid solutions of UICs containing guests from the two classes. This failed, however: solid solution formation of the stacked loop form is usually possible within a series (e.g. with Cl(CH(2))(6)Cl and Br(CH(2))(6)Br), but not between series (e.g. Cl(CH(2))(6)Cl and NC(CH(2))(6)CN). Crystals of Cl(CH(2))(6)CN/urea, in which a single guest contains substituents from each class, are distorted along [001] by only 0.5% from hexagonal symmetry at 298 K and exhibit ferroelastic domain reorientation at high forces. At -66 degrees C, Cl(CH(2))(6)CN/urea undergoes a topotactic phase transition that is unexpectedly nontopochemical. The structure of the low-temperature phase, including the orientation of the methylene chain, closely matches the structures of UICs distorted by 10% along [100] (e.g. Cl(CH(2))(6)Cl/urea). In this transition, small conformation changes of guests give rise to large-scale guest translations of approximately 5.5 A down the channel axis, even though an analogous gauche-to-gauche jump is well established in closely related materials that adopt either high- or low-temperature forms (e.g. NC(CH(2))(6)CN/urea, Cl(CH(2))(6)Cl/urea). The large guest displacement during this transition explains the difficulty in preparing solid solutions of the P2(1)/n form with guests of formula X(CH(2))(6)Y from two different series (e.g. Cl(CH(2))(6)Cl and NC(CH(2))(6)CN). This failure arises not from the different orientations of guest-induced strain, but from preferential occupation of different sites along the channel by the two types of guests. The subtlety of this process and of the interactions involved highlights the difficulty in using simple considerations of isomorphism to design new materials.