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PreprintCC BY-NCChemRxiv

Strategy for the activation of porous molecular crystals using organic vapors

Abstract

Porous molecular crystals (PMCs), i.e., crystalline solids with permanent, virtual, or flexible porosity, are usually synthesized by crystallization from solution, with the solvated molecules included in the pores as guests. To use such crystals as porous materials, the guest molecules must be removed. Typically, thermal treatment is used to promote their desorption, but this method often leads to the loss of crystallinity and catastrophic collapse of the porous structures due to the weakness of the intermolecular interactions. Therefore, methods for guest desorption under mild conditions are in high demand. The present study reports exposure to organic vapors as an unprecedented strategy for this purpose. Specifically, we demonstrate that exposure to vapors of dimethyl sulfoxide, n-butanol, or tert-butanol at room temperature can induce the removal of ethanol molecules encapsulated in crystalline phenylbis(benzothiazol-2-yl)methanol while maintaining its single-crystallinity. Furthermore, this method was found to be applicable for guest desorption from a hydrogen-bonded organic framework based on phenylbis(benzimidazol-2-yl)methanol.

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BibTeX
@misc{murakami2026strategy,
  title = {{Strategy for the activation of porous molecular crystals using organic vapors}},
  author = {Tatsunari Murakami and Kanato Ohgaki and Masaaki Okazaki and Shun Ohta},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010315/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010315/v1},
  note = {CC BY-NC},
}
RIS
TY  - UNPB
TI  - Strategy for the activation of porous molecular crystals using organic vapors
AU  - Tatsunari Murakami
AU  - Kanato Ohgaki
AU  - Masaaki Okazaki
AU  - Shun Ohta
PY  - 2026
DA  - 2026/10/12
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010315/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010315/v1
AB  - Porous molecular crystals (PMCs), i.e., crystalline solids with permanent, virtual, or flexible porosity, are usually synthesized by crystallization from solution, with the solvated molecules included in the pores as guests. To use such crystals as porous materials, the guest molecules must be removed. Typically, thermal treatment is used to promote their desorption, but this method often leads to the loss of crystallinity and catastrophic collapse of the porous structures due to the weakness of the intermolecular interactions. Therefore, methods for guest desorption under mild conditions are in high demand. The present study reports exposure to organic vapors as an unprecedented strategy for this purpose. Specifically, we demonstrate that exposure to vapors of dimethyl sulfoxide, n-butanol, or tert-butanol at room temperature can induce the removal of ethanol molecules encapsulated in crystalline phenylbis(benzothiazol-2-yl)methanol while maintaining its single-crystallinity. Furthermore, this method was found to be applicable for guest desorption from a hydrogen-bonded organic framework based on phenylbis(benzimidazol-2-yl)methanol.
ER  -