A theoretical framework for the design of molecular crystal engines.

Photomechanical molecular crystals have garnered attention for their ability to transform light into mechanical work, but difficulties in characterizing the structural changes and mechanical responses experimentally have hindered the development of practical organic crystal engines. This study proposes a new computational framework for predicting the solid-state crystal-to-crystal photochemical transformations entirely from first principles, and it establishes a photomechanical engine cycle that quantifies the anisotropic mechanical performance resulting from the transformation. The approach relies on crystal structure prediction, solid-state topochemical principles, and high-quality electronic structure methods. After validating the framework on the well-studied [4 + 4] cycloadditions in 9-methyl anthracene and 9-tert-butyl anthracene ester, the experimentally-unknown solid-state transformation of 9-carboxylic acid anthracene is predicted for the first time. The results illustrate how the mechanical work is done by relaxation of the crystal lattice to accommodate the photoproduct, rather than by the photochemistry itself. The large ∼107 J m-3 work densities computed for all three systems highlight the promise of photomechanical crystal engines. This study demonstrates the importance of crystal packing in determining molecular crystal engine performance and provides tools and insights to design improved materials in silico.

Patterning submicron photomechanical features into single diarylethene crystals using electron beam lithography.

Lithography methods are commonly used to create structures in inorganic semiconductors like silicon but have not been widely applied to organic crystals. In this work, electron beam lithography (EBL) is used to pattern structures into single organic photomechanical crystals composed of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene. The electron beam creates amorphous regions of decomposed molecules, while the reactivity of the unexposed crystal regions is preserved under a removable Au coating. Exposure of the patterned crystal to 365 nm light causes ridges of amorphous material to increase in height by 30-70%. This height increase can be reversed by visible light exposure and undergo multiple cycles. The reversible surface morphology changes are strong enough to rupture a sheet of graphene placed on top of the patterned crystal. Surprisingly, the change in dimensions of the EBL features is an order of magnitude larger than the changes in overall crystal dimensions as deduced from X-ray diffraction experiments and microscopy observations. A dynamic extrusion model is presented to explain how nanoscale features imprinted into single crystals can amplify molecular-level photomechanical changes. This work demonstrates the capability of EBL methods to produce sub-micron structural features on single photomechanical crystals, providing a new route to monolithic light-powered actuator devices.

Rational Design, Synthesis, and Biological Evaluation of Fluorine- and Chlorine-Substituted Pyrazol-5-yl-benzamide Derivatives as Potential Succinate Dehydrogenase Inhibitors.

To develop novel succinate dehydrogenase inhibitors (SDHIs), two series of novel N-4-fluoro-pyrazol-5-yl-benzamide and N-4-chloro-pyrazol-5-yl-benzamide derivatives were designed and synthesized, and their antifungal activities were evaluated against Valsa mali, Sclerotinia sclerotiorum, FusaHum graminearum Sehw, Physalospora piricola, and Botrytis cinerea. The bioassay results showed that some of the target compounds exhibited good antifungal activities in vitro against V. mali and S. sclerotiorum. Remarkably, compound 9Ip displayed good in vitro activity against V. mali with an EC50 value of 0.58 mg/L. This outcome was 21-fold greater than that of fluxapyroxad (12.45 mg/L) and close to that of the commercial fungicide tebuconazole (EC50 = 0.36 mg/L). In addition, in vivo experiments proved that compound 9Ip has good protective fungicidal activity with an inhibitory rate of 93.2% against V. mali at 50 mg/L, which was equivalent to that of the positive control tebuconazole (95.5%). The results of molecular docking indicated that there were obvious hydrogen bonds and p-π interactions between compound 9Ip and succinate dehydrogenase (SDH), which could explain the probable action mechanism. In addition, the SDH enzymatic inhibition assay was carried out to further prove its mode of action. Our studies suggest that compound 9Ip could be a fungicidal lead to discover more potent SDHIs for crop protection.

Molecular Crystal Microcapsules: Formation of Sealed Hollow Chambers via Surfactant-Mediated Growth.

Hollow organic molecular cocrystals comprised of 9-methylanthracene-1,2,4,5-tetracyanobenzene (9MA-TCNB) and naphthalene-1,2,4,5-tetracyanobenzene (NAPH-TCNB) were fabricated using a surfactant-mediated co-reprecipitation method. The crystals exhibit a narrow size distribution that can be easily tuned by varying the concentration of surfactant and incubation temperature. The rectangular crystals possess symmetrical twinned cavities with an estimated storage volume on the order of 10-10  L. An aqueous dye solution can be incorporated into the cavities during crystal growth and stored inside for up to several hours, confirming the sealed nature of the hollow chambers. Our results demonstrate that it is possible to harness non-classical crystal growth to fabricate organic molecular crystals with novel topologies.

Covalent Atomic Bridges Enable Unidirectional Enhancement of Electronic Transport in Aligned Carbon Nanotubes.

Interconnecting the surfaces of nanomaterials without compromising their outstanding mechanical, thermal, and electronic properties is critical in the design of advanced bulk structures that still preserve the novel properties of their nanoscale constituents. As such, bridging the π-conjugated carbon surfaces of single-walled carbon nanotubes (SWNTs) has special implications in next-generation electronics. This study presents a rational path toward the improvement of the electrical transport in aligned semiconducting SWNT films by deposition of metal atoms. The formation of conducting Cr-mediated pathways between the parallel SWNTs increases the transverse (intertube) conductance while having a negligible effect on the parallel (intratube) transport. In contrast, doping with Li has a predominant effect on the intratube electrical transport of aligned SWNT films. Large-scale first-principles calculations of electrical transport on aligned SWNTs show good agreement with the experimental electrical measurements and provide insight into the changes that different metal atoms exert on the density of states near the Fermi level of the SWNTs and the formation of transport channels.

Protection of Molecular Microcrystals by Encapsulation under Single-Layer Graphene.

Microcrystals composed of the conjugated organic molecule perylene can be encapsulated beneath single-layer graphene using mild conditions. Scanning electron and atomic force microscopy images show that the graphene exists as a conformal coating on top of the crystal. Raman spectroscopy indicates that the graphene is only slightly perturbed by the underlying crystal, probably due to strain. The graphene layer provides complete protection from a variety of solvents and prevents sublimation of the crystal at elevated temperatures. Time-resolved photoluminescence measurements do not detect any quenching of the perylene emission by the graphene layer, although nonradiative energy transfer within a few nanometers of the crystal-graphene interface cannot be ruled out. The ability to encapsulate samples on a substrate under a graphene monolayer may provide a new way to access and interact with the organic crystal under ambient conditions.

Sublimation-assisted graphene transfer technique based on small polyaromatic hydrocarbons.

Advances in the chemical vapor deposition (CVD) growth of graphene have made this material a very attractive candidate for a number of applications including transparent conductors, electronics, optoeletronics, biomedical devices and energy storage. The CVD method requires transfer of graphene on a desired substrate and this is most commonly accomplished with polymers. The removal of polymer carriers is achieved with organic solvents or thermal treatment which makes this approach inappropriate for application to plastic thin films such as polyethylene terephthalate substrates. An ultraclean graphene transfer method under mild conditions is highly desired. In this article, we report a naphthalene-assisted graphene transfer technique which provides a reliable route to residue-free transfer of graphene to both hard and flexible substrates. The quality of the transferred graphene was characterized with atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. Field effect transistors, based on the naphthalene-transfered graphene, were fabricated and characterized. This work has the potential to broaden the applications of CVD graphene in fields where ultraclean graphene and mild graphene transfer conditions are required.