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Adaptive crystals have attracted significant attention from solid-state chemists and crystal engineers for their promising applications in memories, capacitors, sensors, and actuators. Among them, thermosalient crystals are particularly favored thanks to their efficient energy conversions and rapid responses. However, the mechanisms for the mechanical responses of thermosalient crystals remain largely unclear. Herein we demonstrate that thermosalient effects of molecular crystals could be driven by thermoelastic twisting behaviors. The crystal, based on a model compound with rigid dibenzothiophene sulfone planes and flexible ethoxy chains, can spontaneously self-heal from mechanical fractures. Upon heating, the crystal undergoes remarkable thermosalient behaviors driven by a distinctive left- or right-handed twisting. This thermoelastic twisting converts thermal energy into elastic potential energy, which is further released as kinetic energy upon untwisting to drive the crystal jump. Our demonstration on thermoelastic twisting-induced crystal jumping offers a different perspective on the origins of thermosalient crystals and could provide inspiration for future engineering and application of dynamic molecular crystals.
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http://dx.doi.org/10.1073/pnas.2417901122 | DOI Listing |
Small
August 2025
National Engineering Research Center of Industrial Crystallization Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China.
Dynamic crystals, characterized by their rapid response speed, diverse response forms, and lightweight, have emerged as promising material platforms for developing next-generation adaptive devices. Herein, a thermosalient cocrystal is developed, which possesses both mechanical flexibility and reversible phase transition capability. Remarkably, the crystal exhibits thermosalient phenomenon in the near-human body temperature range, and its excellent flexibility ensures structural robustness throughout the phase transition process.
View Article and Find Full Text PDFChem Mater
May 2025
Instituto de Química (IQ), Universidad Nacional Autónoma de México (UNAM), Circuito Exterior s/n, Ciudad Universitaria, Coyoacán, Ciudad de México 04510, México.
The thermosalient effect is a rarely observed, potentially very useful and at the present, unpredictable mechanical response during a phase transition that is thought to hold the potential for rapid and clean energy conversion devoid of gaseous products. Here, we report the serendipitous discovery of a rare instance of a thermosalient organic solid that exhibits the effect below room temperature. The crystals of this carbazole-based material are dynamic at both molecular and macroscopic scales.
View Article and Find Full Text PDFJ Am Chem Soc
April 2025
Department of Chemical Sciences, University of Naples Federico II, Via Cintia, I-80126 Naples, Italy.
Thermosalient transitions are a subset of single-crystal-to-single-crystal (SCSC) transitions, in which the change of lattice parameters is highly anisotropic and very fast. As a result, crystals at the transition undergo macroscopic dynamical effects (hopping, jumping, and shattering). These transitions feature a conversion of heat to mechanical energy that can be exploited in the realization of advanced materials.
View Article and Find Full Text PDFAdv Sci (Weinh)
July 2025
Department of Pharmaceutics, School of Pharmacy, China Pharmaceutical University, Nanjing, 211198, P. R. China.
Thermally responsive molecular crystals exhibiting programmable mechanical motions hold significant promise for applications in smart actuators, sensors, and drug delivery systems. However, achieving precise control over their phase transition thermodynamics remains a fundamental challenge. A series of isomorphic 5-fluorocytosine/fatty acid cocrystals is reported where the phase transition temperatures vary across an interval of 100 K with increasing alkyl chain.
View Article and Find Full Text PDFJ Am Chem Soc
March 2025
Australian Synchrotron, Australian Nuclear Science and Technology Organisation, Lucas Heights, New South Wales 2234, Australia.
The thermosalient transformation in nickel(II) bis(diisopropyl)dithiocarbamate has been investigated using selective deuteration. The deuterated crystals undergo a reversible displacive phase transition that is ∼4 K higher in temperature compared to the protonated analogue. Neutron, synchrotron, density-functional theory, and calorimetric techniques were utilized to demonstrate the substantial effect of deuterium.
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