The Ward group in the Department of Chemistry is a highly interdisciplinary research group at the intersection of organic solid-state chemistry, physical chemistry, materials science, and biomedical chemistry.
In a special issue dedicated to Martin Pope, a pioneer of organic electronics, graduate studnets Anna Yusov and Alexandra Dillon report that guanidinium organosulfonate (GS) hydrogen-bonded frameworks (HBFs) constructed from three different naphthalenesulfonates incorporate the electron acceptor tetracyanoquinodimethane (TCNQ) as a guest molecule, with framework architectures that reflect synergy between the persistent 2D hydrogen-bonded GS network and donor-acceptor interactions. The spectroscopic and computational results confirm weak charge-transfer interactions associated with the formation of mixed stacks containing naphthalene donors and TCNQ acceptors that are enforced by the GS framework, suggesting opportunities for the synthesis of new optoelectronic materials through a combination of molecular and crystal design. Find the article here.
Crystallization from the melt can allow the achievement of high driving force for crystallization accompanied by relatively slow growth, nucleation, and transformation rates, features that favor its use as an efficient polymorph screening method. Surprisingly, even though melt crystallization has a long history, it has been employed less often in the search for new polymorphs than solution crystallization. In a study of 21 well-characterized compounds with at least five ambient polymorphs, MDI investigators found that melt crystallization afforded more than half of the known polymorphs and in many cases revealed new polymorphs not detected by other screening methods. A statistical analysis revealed that polymorphs grown from the melt have a greater propensity for high Z′ values, which are not easily accessible by other crystallization protocols and are often not detectable by crystal structure prediction methods. Melt crystallization within nanopores (8–100 nm) performed for 19 of the 21 compounds mostly resulted in polymorphs that dominated crystallization from the bulk melt at similar temperatures. The total number of polymorphs observed in nanopores was less than that observed during crystallization from the bulk melt, however, and melt crystallization under confinement revealed new polymorphs not detected by other crystallization methods. Find the article here.
MDI investigators, including graduate students Fangyuan Dong, Samira Munkaila and Veronica Grebe, devised a synthetic strategy for fabricating colloidal particles with spatially segregated amine-functionalized lobes enables regioselective coating with gold to afford metallodielectric particles with a variety of shapes and lobe sizes. This approach can produce either dissymmetric dumbbell-shaped two-lobed Au-TPM particles (Au-T) or dissymmetric or symmetric three-lobed particles with gold coating on one (Au-T-T and T-Au-T) or two lobes (Au-T-Au). Dielectrophoretic (DEP) forces exerted by an AC field confined between two opposing electrodes generate aggregates ranging from 1D chains to 2D close-packed lattices, depending on the particle shape and lobe arrangement. The aggregate structures reflect the lowest energy configurations resulting from the induced dipole moments created in particle lobes within the confined electric field. Find the article here.
MDI investigators previously discovered that the efficacy of crystalline contact insecticides depends on the crystalline form (a.k.a. polymorphs). Polymorphism in contact insecticides, however, and its importance to efficacy, was largely unknown to the vector control community. Crystallographic characterization of contact insecticide solids needs to be systematic to identify more active solid forms. Here, the investigators report seven new crystal structures, mostly pyrethroid insecticides recommended by the WHO for indoor residual spraying, as well as a new form of a neonicotinoid insecticide. These results further highlight polymorphism in contact insecticides.