TY - JOUR
T1 - Exploration of glassy state in Prussian blue analogues
AU - Ma, Nattapol
AU - Ohtani, Ryo
AU - Le, Hung M.
AU - Sørensen, Søren Strandskov
AU - Ishikawa, Ryuta
AU - Kawata, Satoshi
AU - Bureekaew, Sareeya
AU - Kosasang, Soracha
AU - Kawazoe, Yoshiyuki
AU - Ohara, Koji
AU - Smedskjær, Morten Mattrup
AU - Horike, Satoshi
N1 - © 2022. The Author(s).
PY - 2022/12
Y1 - 2022/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85133905837&partnerID=8YFLogxK
U2 - 10.1038/s41467-022-31658-w
DO - 10.1038/s41467-022-31658-w
M3 - Journal article
C2 - 35821027
SN - 2041-1723
VL - 13
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 4023
ER -