Bottom-Up Synthesis of Crystalline Covalent Organic Framework Nanosheets, Nanotubes, and Kippah Vesicles: An Odd-Even Effect Induction

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Kalipada Koner - , Indian Institute of Science Education and Research, Kolkata (Author)
  • Arnab Sadhukhan - , Indian Institute of Science Education and Research, Kolkata (Author)
  • Suvendu Karak - , Indian Institute of Science Education and Research, Kolkata (Author)
  • Himadri Sekhar Sasmal - , Indian Institute of Science Education and Research, Kolkata (Author)
  • Yutaro Ogaeri - , JEOL Ltd. (Author)
  • Yusuke Nishiyama - , JEOL Ltd. (Author)
  • Shuangjie Zhao - , Faculty of Chemistry and Food Chemistry (Author)
  • Miroslav Položij - , Faculty of Chemistry and Food Chemistry, Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Agnieszka Kuc - , Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Thomas Heine - , Faculty of Chemistry and Food Chemistry, Helmholtz-Zentrum Dresden-Rossendorf, Yonsei University (Author)
  • Rahul Banerjee - , Indian Institute of Science Education and Research, Kolkata (Author)

Abstract

Few-layer organic nanosheets are becoming increasingly attractive as two-dimensional (2D) materials due to their precise atomic connectivity and tailor-made pores. However, most strategies for synthesizing nanosheets rely on surface-assisted methods or top-down exfoliation of stacked materials. A bottom-up approach with well-designed building blocks would be the convenient pathway to achieve the bulk-scale synthesis of 2D nanosheets with uniform size and crystallinity. Herein, we have synthesized crystalline covalent organic framework nanosheets (CONs) by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines. The bent geometry of thianthrene in THT retards the out-of-plane stacking, while the flexible diamines introduce dynamic characteristics into the framework, facilitating nanosheet formation. Successful isoreticulation with five diamines with two to six carbon chain lengths generalizes the design strategy. Microscopic imaging reveals that the odd and even diamine-based CONs transmute to different nanostructures, such as nanotubes and hollow spheres. The single-crystal X-ray diffraction structure of repeating units indicates that the odd-even linker units of diamines introduce irregular-regular curvature in the backbone, aiding such dimensionality conversion. Theoretical calculations shed more light on nanosheet stacking and rolling behavior with respect to the odd-even effects.

Details

Original languageEnglish
Pages (from-to)14475-14483
Number of pages9
JournalJournal of the American Chemical Society
Volume145
Issue number26
Publication statusPublished - 5 Jul 2023
Peer-reviewedYes

External IDs

PubMed 37339245
WOS 001016732700001

Keywords

Keywords

  • Surface synthesis, Exfoliation