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Switchable colossal anisotropic thermal expansion in a spin crossover framework.

Si-Guo Wu1, Wen Cui1, Ze-Yu Ruan1

  • 1Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, Sun Yat-Sen University Guangzhou 510006 P. R. China nizhp@mail.sysu.edu.cn tongml@mail.sysu.edu.cn.

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Summary

Researchers developed a novel dynamic crystal material exhibiting switchable colossal anisotropic thermal expansion (ATE). This material shows potential for advanced thermomechanical sensing applications by combining vibrational and electronic mechanisms for tunable thermal properties.

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Area of Science:

  • Materials Science
  • Crystallography
  • Supramolecular Chemistry

Background:

  • Advanced materials with tunable thermal expansion are crucial for thermomechanical sensing and thermal stress resistance.
  • Hofmann-type frameworks offer a versatile platform for designing functional materials.

Purpose of the Study:

  • To realize switchable colossal anisotropic thermal expansion (ATE) in a Hofmann-type framework.
  • To investigate the mechanisms driving ATE behavior through a combined vibrational, electronic, and molecular motion strategy.
  • To demonstrate the potential of dynamic crystal materials for tunable thermomechanical properties.

Main Methods:

  • Synthesis of a Hofmann-type framework: [Fe(bpy-NH2){Au(CN)2}2]·iPrOH.
  • Investigation of structural deformations driven by host-guest interactions.
  • Analysis of thermal expansion behavior using a combination of vibrational and electronic mechanisms.
  • Characterization of spin crossover (SCO) phenomena and its correlation with thermal expansion.

Main Results:

  • Switchable colossal anisotropic thermal expansion (ATE) was achieved in the Fe·iPrOH framework.
  • A scissor-like motion within rhombic grids, driven by dicyanoaurate rotation, led to colossal ATE.
  • Reverse ATE behavior was observed due to spin transition, host-guest cooperation, and molecular motion of iPrOH guests.
  • A high negative thermal expansion coefficient of -7.49 × 10^5 M K^-1 was recorded alongside abrupt SCO behavior.

Conclusions:

  • The study presents a novel strategy for designing dynamic crystal materials with tunable thermomechanical properties.
  • Integrating multiple ATE-related elements into a unified platform enables switchable and colossal thermal expansion.
  • The findings offer new perspectives for developing advanced materials for thermomechanical sensing and stress management.