Unraveling two distinct polymorph transition mechanisms in one n-type single crystal for dynamic electronics.

Cooperativity is used by living systems to circumvent energetic and entropic barriers to yield highly efficient molecular processes. Cooperative structural transitions involve the concerted displacement of molecules in a crystalline material, as opposed to typical molecule-by-molecule nucleation and growth mechanisms which often break single crystallinity. Cooperative transitions have acquired much attention for low transition barriers, ultrafast kinetics, and structural reversibility. However, cooperative transitions are rare in molecular crystals and their origin is poorly understood. Crystals of 2-dimensional quinoidal terthiophene (2DQTT-o-B), a high-performance n-type organic semiconductor, demonstrate two distinct thermally activated phase transitions following these mechanisms. Here we show reorientation of the alkyl side chains triggers cooperative behavior, tilting the molecules like dominos. Whereas, nucleation and growth transition is coincident with increasing alkyl chain disorder and driven by forming a biradical state. We establish alkyl chain engineering as integral to rationally controlling these polymorphic behaviors for novel electronic applications.

Evidence That Less Can Be More for Transferable Force Fields.

Graph-based parameter assignment has been the basis for developing transferable force fields for molecular dynamics simulations for decades. Nevertheless, transferable force fields vary in how specifically terms are defined with respect to the molecular graph and the procedures for generating parametrization data. More-specific force-field terms increase the complexity of the force field, theoretically increasing accuracy but also increasing training data requirements. In contrast, less-specific force fields can be reused across larger regions of chemical space, theoretically reducing accuracy but also reducing the number of parameters and training data requirements. Here, the tradeoffs between force-field specificity and accuracy are quantified by parametrizing three new sets of force fields with varying levels of graph specificity, using a shared procedure for generating training data. These force fields are benchmarked for their ability to reproduce the structural features and liquid properties of 87 organic molecules at 146 distinct state points. The overall accuracy for properties that were directly trained on rapidly saturates as the graph specificity of the force-field increases. From this, we conclude there is at best a marginal benefit of using less transferable and more complex force fields with common sources of quantum-chemically derived training data. When looking at properties unseen during training, there is some evidence that the more-complex force fields even perform slightly worse. These results are rationalized by the fortuitous regularization of force fields based on less-specific and more-transferable atom types. Both the saturation in the accuracy of training properties and the marginally worse performance on off-target properties fundamentally contradict the expectation that bespoke force fields are generally more accurate, given their larger number of parameters, and suggests that increasing force-field complexity should be carefully justified against performance gains and balanced against available training data.

Side-Chain Control of Topochemical Polymer Single Crystals with Tunable Elastic Modulus.

Topochemical polymerizations hold the promise of producing high molecular weight and stereoregular single crystalline polymers by first aligning monomers before polymerization. However, monomer modifications often alter the crystal packing and result in non-reactive polymorphs. Here, we report a systematic study on the side chain functionalization of the bis(indandione) derivative system that can be polymerized under visible light. Precisely engineered side chains help organize the monomer crystals in a one-dimensional fashion to maintain the topochemical reactivity. By optimizing the side chain length and end group of monomers, the elastic modulus of the resulting polymer single crystals can also be greatly enhanced. Lastly, using ultrasonication, insoluble polymer single crystals can be processed into free-standing and robust polymer thin films. This work provides new insights on the molecular design of topochemical reactions and paves the way for future applications of this fascinating family of materials.

Ion-Solvent Interplay in Concentrated Electrolytes Enables Subzero Temperature Li-Ion Battery Operations.

Despite the essential role of ethylene carbonate (EC) in solid electrolyte interphase (SEI) formation, the high Li+ desolvation barrier and melting point (36 °C) of EC impede lithium-ion battery operation at low temperatures and induce sluggish Li+ reaction kinetics. Here, we demonstrate an EC-free high salt concentration electrolyte (HSCE) composed of lithium bis(fluorosulfonyl)imide salt and tetrahydrofuran solvent with enhanced subzero temperature operation originating from unusually rapid low-temperature Li+ transport. Experimental and theoretical characterizations reveal the dominance of intra-aggregate ion transport in the HSCE that enables efficient low-temperature transport by increasing the exchange rate of solvating counterions relative to that of solvent molecules. This electrolyte also produces a <5 nm thick anion-derived LiF-rich SEI layer with excellent graphite electrode compatibility and electrochemical performance at subzero temperature in half-cells. Full cells based on LiNi0.6Co0.2Mn0.2O2||graphite with tailored HSCE electrolytes outperform state-of-the-art cells comprising conventional EC electrolytes during charge-discharge operation at an extreme temperature of -40 °C. These results demonstrate the opportunities for creating intrinsically robust low-temperature Li+ technology.

Circularly Recyclable Polymers Featuring Topochemically Weakened Carbon-Carbon Bonds.

Closed-loop circular utilization of plastics is of manifold significance, yet energy-intensive and poorly selective scission of the ubiquitous carbon-carbon (C-C) bonds in contemporary commercial polymers pose tremendous challenges to envisioned recycling and upcycling scenarios. Here, we demonstrate a topochemical approach for creating elongated C-C bonds with a bond length of 1.57∼1.63 Å between repeating units in the solid state with decreased bond dissociation energies. Elongated bonds were introduced between the repeating units of 12 distinct polymers from three classes. In all cases, the materials exhibit rapid depolymerization via breakage of the elongated bond within a desirable temperature range (140∼260 °C) while otherwise remaining remarkably stable under harsh conditions. Furthermore, the topochemically prepared polymers are processable and 3D-printable while maintaining a high depolymerization yield and tunable mechanical properties. These results suggest that the crystalline polymers synthesized from simple photochemistry and without expensive catalysts are promising for practical applications with complete materials' circularity.

Topology Automated Force-Field Interactions (TAFFI): A Framework for Developing Transferable Force Fields.

Force-field development has undergone a revolution in the past decade with the proliferation of quantum chemistry based parametrizations and the introduction of machine learning approximations of the atomistic potential energy surface. Nevertheless, transferable force fields with broad coverage of organic chemical space remain necessary for applications in materials and chemical discovery where throughput, consistency, and computational cost are paramount. Here, we introduce a force-field development framework called Topology Automated Force-Field Interactions (TAFFI) for developing transferable force fields of varying complexity against an extensible database of quantum chemistry calculations. TAFFI formalizes the concept of atom typing and makes it the basis for generating systematic training data that maintains a one-to-one correspondence with force-field terms. This feature makes TAFFI arbitrarily extensible to new chemistries while maintaining internal consistency and transferability. As a demonstration of TAFFI, we have developed a fixed-charge force-field, TAFFI-gen, from scratch that includes coverage for common organic functional groups that is comparable to established transferable force fields. The performance of TAFFI-gen was benchmarked against OPLS and GAFF for reproducing several experimental properties of 87 organic liquids. The consistent performance of these force fields, despite their distinct origins, validates the TAFFI framework while also providing evidence of the representability limitations of fixed-charge force fields.

Enhanced sampling of cylindrical microphase separation via a shell-averaged bond-orientational order parameter.

The formation of a hexagonal phase from disordered phase is one of the typical order-disorder transitions (ODTs) observed in asymmetric diblock copolymer systems. In order to drive this transition in a particle-based simulation, we introduce a shell-based bond-orientational order parameter that selectively responds to the mesoscopic order of the hexagonal cylinder phase. From metadynamics simulations in a bond-free particle model system, the characteristic pathway involved with the underlying free energy surface is deduced for the disordered-to-hexagonal transition. It is shown consecutively that the transition pathway and the metastable state are reproduced in dissipative particle dynamics simulations for the corresponding transition in a bulk asymmetric block copolymer melt system. These agreements suggest that efficient strategies for enhanced sampling with particle-based simulations of block copolymer systems can be devised using coarse-grained pictures of the mesoscopic order.

Effect of hydrothermal processing on ginseng extract.

BACKGROUND: Panax ginseng Meyer is cultivated because of its medicinal effects on the immune system, blood pressure, and cancer. Major ginsenosides in fresh ginseng are converted to minor ginsenosides by structural changes such as hydrolysis and dehydration. The transformed ginsenosides are generally more bioavailable and bioactive than the primary ginsenosides. Therefore, in this study, hydrothermal processing was applied to ginseng preparation to increase the yields of the transformed ginsenosides, such as 20(S)-Rg3, Rk1, and Rg5, and enhance antioxidant activities in an effective way. METHODS: Ginseng extract was hydrothermally processed using batch reactors at 100-160°C with differing reaction times. Quantitative analysis of the ginsenoside yields was performed using HPLC, and the antioxidant activity was qualitatively analyzed by evaluating 2,2'-azino-bis radical cation scavenging, 2,2-diphenyl-1-picrylhydrazyl radical scavenging, and phenolic antioxidants. Red ginseng and sun ginseng were prepared by conventional steaming as the control group. RESULTS: Unlike steaming, the hydrothermal process was performed under homogeneous conditions. Chemical reaction, heat transfer, and mass transfer are generally more efficient in homogeneous reactions. Therefore, maximum yields for the hydrothermal process were 2.5-25 times higher than those for steaming, and the antioxidant activities showed 1.6-4-fold increases for the hydrothermal process. Moreover, the reaction time was decreased from 3 h to 15-35 min using hydrothermal processing. CONCLUSION: Therefore, hydrothermal processing offers significant improvements over the conventional steaming process. In particular, at temperatures over 140°C, high yields of the transformed ginsenosides and increased antioxidant activities were obtained in tens of minutes.