Oral Presentation Royal Australian Chemical Institute National Congress 2026

Dual-responsive chiroptical properties in a cofacial TTF-based metal-organic framework (136559)

Katelyn M Clutterbuck 1 2 , Girish Lakhwani 2 , Deanna M D'Alessandro 1
  1. School of Chemical and Biomolecular Engineering, The University of Sydney, Darlington, NSW, Australia
  2. School of Chemistry, The University of Sydney, Camperdown, NSW, Australia

Stimuli-responsive chiroptical properties in materials are critical to the development of next generation security, biological sensing, 3-D display and data storage materials.[1] Current chiral materials are however limited in their device application due to their low chiroptical responses and a lack of specific control over the response. Chiral Metal-Organic Frameworks (MOFs) may overcome these limitations due their ability to generate supramolecular chirality which can increase chiroptical response.[2] Additionally, MOFs may exhibit properties additional or different to those of their component metal-ions and bridging ligands due to their ability to hold them in a particular orientation within a framework. MOFs containing TTF-based ligands demonstrate potential as dual-responsive materials due to their ability to undergo a light-induced [2+2] cycloaddition when co-facially arranged, and their susceptibility to oxidation.[3,4] We aim to develop multi-stimuli responsive chiral MOFs through the incorporation of TTF-based ligands and chiral co-ligands with an outlook for their use as logic gate materials.

We report the synthesis, structure and switching properties of a Cd-based MOF containing chiral camphorate and achiral 2,6-bis(4′-pyridyl)-tetrathiafulvalene (Py2TTF) ligands. X-ray diffraction studies elucidated the co-facial arrangement of the Py2TTF ligands, enabling the framework to undergo the [2+2] photocyclisation process, which is reversible with heating. Additionally, the reversible oxidation of the TTF moieties was investigated. Both switching techniques showed responsiveness to both the MOF’s optical and chiroptical spectra. Results demonstrate the viability of this MOF for future applications as logic gates in optoelectronic devices.

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  2. 2. J. L. Greenfield et. al., Chem. Sci, 12, 8589, (2021).
  3. 3. D. A. Sherman et. al., Nat. Commun., 11, 2808, (2020).
  4. 4. E. K. Kearns et. al., Mater. Adv., 5, 1588, (2024).