Exploration of glassy state in Prussian blue analogues

Nattapol Ma, Ryo Ohtani, Hung M. Le, Søren S. Sørensen, Ryuta Ishikawa, Satoshi Kawata, Sareeya Bureekaew, Soracha Kosasang, Yoshiyuki Kawazoe, Koji Ohara, Morten M. Smedskjaer, Satoshi Horike

研究成果: ジャーナルへの寄稿学術誌査読


Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal–organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal–ligand–metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.

ジャーナルNature communications
出版ステータス出版済み - 12月 2022

!!!All Science Journal Classification (ASJC) codes

  • 化学 (全般)
  • 生化学、遺伝学、分子生物学(全般)
  • 一般
  • 物理学および天文学(全般)


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