Dislocations in molecular crystals.

Dislocations in molecular crystals remain terra incognita. Owing to the complexity of molecular structure, dislocations in molecular crystals can be difficult to understand using only the foundational concepts devised over decades for hard materials. Herein, we review the generation, structure, and physicochemical consequences of dislocations in molecular crystals. Unlike metals, ceramics, and semiconductors, molecular crystals are often characterized by flexible building units of low symmetry, thereby limiting analysis, complicating modeling, and prompting new approaches to elucidate their role in crystallography from growth to mechanics. Such considerations affect applications ranging from plastic electronics and mechanical actuators to the tableting of pharmaceuticals.

Measurement of heterogeneous reaction rates: three strategies for controlling mass transport and their application to indium-mediated allylations.

We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics.

Measurement of heterogeneous reaction rates during indium-mediated allylation.

Indium-mediated allylation provides remarkable stereo- and regioselectivity, and it proceeds easily and in high yield in aqueous solutions. In spite of its widespread use, there have been few fundamental studies of this reaction. We have developed a photomicrographic technique for measuring rates of reaction of allyl halides at indium surfaces, and we describe the mathematical model for discriminating between diffusion and kinetic control. The measurements demonstrate that this reaction is diffusion controlled, and the minimum value of the heterogeneous rate constant is 1 x 10(-3) cm s(-1). These results broaden the applicability of photomicroscopy for measuring heterogeneous rates of reactions that result in consumption of solid metals.

Structure, Energetics, and Dynamics of Screw Dislocations in Even n-Alkane Crystals.

Spiral hillocks on n-alkane crystal surfaces were observed immediately after Frank recognized the importance of screw dislocations for crystal growth, yet their structures and energies in molecular crystals remain ill-defined. To illustrate the structural chemistry of screw dislocations that are responsible for plasticity in organic crystals and upon which the organic electronics and pharmaceutical industries depend, molecular dynamics was used to examine heterochiral dislocation pairs with Burgers vectors along [001] in n-hexane, n-octane, and n-decane crystals. The cores were anisotropic and elongated in the (110) slip plane, with significant local changes in molecular position, orientation, conformation, and energy. This detailed atomic level picture produced a distribution of strain consistent with linear elastic theory, giving confidence in the simulations. Dislocations with doubled Burgers vectors split into pairs with elementary displacements. These results suggest a pathway to understanding the mechanical properties and failure associated with elastic and plastic deformation in soft crystals.