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The temperature-composition phase diagram of two solids, A and B, which are immiscible in the solid phase but form miscible liquids, shows that when the temperature is low, these two exist as separate, pure solids (A and B). As the temperature increases, they transition into a single-phase liquid solution where A and B coexist. Moving from point a1 to a2 in the phase diagram, the composition changes such that solid B begins to separate from the solution, enriching the remaining liquid with A.
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Researchers developed novel molecular crystals that move when heated. These crystals release solvents, enabling controllable mechanical responses for advanced energy materials.

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Area of Science:

  • Materials Science
  • Crystallography
  • Supramolecular Chemistry

Background:

  • Harnessing mechanical motion in molecular crystals is key for new energy conversion materials.
  • The jumping-mate approach, involving guest molecule ejection, offers direct propulsion.
  • Isostructural cocrystals provide a platform for studying guest-host interactions and mechanical responses.

Purpose of the Study:

  • To design and synthesize novel cocrystals capable of thermosalient effects.
  • To investigate the role of occluded solvents in triggering mechanical responses.
  • To demonstrate controllable thermal actuation in molecular crystals for energy applications.

Main Methods:

  • Synthesis of isostructural cocrystals of indolo[3,2-a]carbazole (ICZ) and (E)-1,2-di(pyridin-4-yl)ethene (BPE) with various solvents.
  • X-ray diffraction and solid-state nuclear magnetic resonance (NMR) for structural and solvent confirmation.
  • Differential scanning calorimetry and thermogravimetry (DSC-TGA) to analyze thermal transitions and solvent release.

Main Results:

  • Successfully synthesized channel-type cocrystals incorporating acetone, ethyl acetate, or tetrahydrofuran.
  • Observed a thermosalient effect upon heating, characterized by the release of pure solvents or solvent mixtures.
  • Demonstrated progressive changes in transition temperatures, indicating controllable thermal actuation via solvent release.

Conclusions:

  • Developed a simple yet effective method for regulating mechanical responses in molecular crystals.
  • Advanced the design principles for responsive energy conversion materials.
  • Highlighted the potential of guest molecule ejection for controlled mechanical actuation in crystalline solids.