Light and Guest Responsive Behavior in a Porous Coordination Network Enabled by Reversible [2+2] Photocycloaddition

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Mei Yan Gao - , University of Limerick (Author)
  • Lunjie Liu - , Southern University of Science and Technology (Author)
  • Chenghua Deng - , University of Limerick (Author)
  • Volodymyr Bon - , Chair of Inorganic Chemistry I (Author)
  • Bai Qiao Song - , University of Limerick (Author)
  • Sihai Yang - , University of Manchester, Peking University (Author)
  • Martin Schröder - , University of Manchester (Author)
  • Stefan Kaskel - , Chair of Inorganic Chemistry I (Author)
  • Michael J. Zaworotko - , University of Limerick (Author)

Abstract

Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation. Whereas reports on guest or light-responsive sorbents have increased in recent years, we are unaware of reports on sorbents that exhibit both light and guest-induced structural transformations. Herein, we report that the square lattice, sql, topology coordination network Zn(fba)(bis) ⋅ 2DMF (sql-5,6-Zn-α, 5=trans-4,4′-bis(1-imidazolyl)stilbene=bis, 6=2,2-bis(4-carboxyphenyl)hexafluoropropane=H2fba) underwent single-crystal-to-single-crystal transformation (SCSC) upon activation, affording nonporous sql-5,6-Zn-β. Parallel alignment at 3.23 Å of olefinic moieties on adjacent bis ligands in sql-5,6-Zn-α enabled SCSC [2+2] photocycloaddition upon exposure to UV light (365 nm) or sunlight. sql-5,6-Zn-α thereby transformed to mot-5,6-Zn-α, which was subsequently activated to the narrow pore phase mot-5,6-Zn-β. sql-5,6-Zn-β and mot-5,6-Zn-β both exhibited S-shaped adsorption isotherms characteristic of guest-induced structural changes when exposed to CO2 at 195 K (type-F–IV and type F–I, respectively). Cycling experiments conducted upon sql-5,6-Zn-β reduced particle size after cycle 1 and induced transformation into a rare example of a shape memory coordination network, sql-5,6-Zn-γ. Insight into this smorgasbord of SCSC phase changes was gained from in situ PXRD, single crystal XRD and 1H NMR spectroscopy experiments.

Details

Original languageEnglish
Article numbere202404084
JournalAngewandte Chemie - International Edition
Volume63
Issue number34
Publication statusPublished - 19 Aug 2024
Peer-reviewedYes

External IDs

PubMed 38863431

Keywords

ASJC Scopus subject areas

Keywords

  • flexibility, photocycloaddition, porous coordination networks, shape memory, single-crystal-to-single-crystal transformation