Dynamic two-dimensional covalent organic frameworks

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Florian Auras - , Chair of Molecular Functional Materials (cfaed), University of Cambridge, TUD Dresden University of Technology (Author)
  • Laura Ascherl - , Ludwig Maximilian University of Munich (Author)
  • Volodymyr Bon - , Chair of Inorganic Chemistry I (Author)
  • Simon M. Vornholt - , Stony Brook University (Author)
  • Simon Krause - , Chair of Inorganic Chemistry I, Max Planck Institute for Solid State Research (Author)
  • Markus Döblinger - , Ludwig Maximilian University of Munich (Author)
  • Derya Bessinger - , Ludwig Maximilian University of Munich (Author)
  • Stephan Reuter - , Ludwig Maximilian University of Munich (Author)
  • Karena W. Chapman - , Stony Brook University (Author)
  • Stefan Kaskel - , Chair of Inorganic Chemistry I (Author)
  • Richard H. Friend - , University of Cambridge (Author)
  • Thomas Bein - , Ludwig Maximilian University of Munich (Author)

Abstract

Porous covalent organic frameworks (COFs) enable the realization of functional materials with molecular precision. Past research has typically focused on generating rigid frameworks where structural and optoelectronic properties are static. Here we report dynamic two-dimensional (2D) COFs that can open and close their pores upon uptake or removal of guests while retaining their crystalline long-range order. Constructing dynamic, yet crystalline and robust frameworks requires a well-controlled degree of flexibility. We have achieved this through a ‘wine rack’ design where rigid π-stacked columns of perylene diimides are interconnected by non-stacked, flexible bridges. The resulting COFs show stepwise phase transformations between their respective contracted-pore and open-pore conformations with up to 40% increase in unit-cell volume. This variable geometry provides a handle for introducing stimuli-responsive optoelectronic properties. We illustrate this by demonstrating switchable optical absorption and emission characteristics, which approximate ‘null-aggregates’ with monomer-like behaviour in the contracted COFs. This work provides a design strategy for dynamic 2D COFs that are potentially useful for realizing stimuli-responsive materials. (Figure presented.).

Details

Original languageEnglish
JournalNature chemistry
Publication statusAccepted/In press - 2024
Peer-reviewedYes

Keywords