The First Use of a ReX5 Synthon to Modulate FeIII Spin Crossover via Supramolecular Halogen⋅⋅⋅Halogen Interactions

Rebecca Busch; Anthony B Carter; Konstantis F Konidaris; Irina A Kühne; Ricardo González; Christopher E Anson; Annie K Powell

doi:10.1002/chem.202001668

The First Use of a ReX₅ Synthon to Modulate Fe^III Spin Crossover via Supramolecular Halogen⋅⋅⋅Halogen Interactions

Chemistry. 2020 Sep 10;26(51):11835-11840. doi: 10.1002/chem.202001668. Epub 2020 Aug 13.

Authors

Rebecca Busch¹, Anthony B Carter^{1

2}, Konstantis F Konidaris^{1

3}, Irina A Kühne^{1

4}, Ricardo González⁵, Christopher E Anson¹, Annie K Powell^{1

6}

Affiliations

¹ Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131, Karlsruhe, Germany.
² School of Chemistry, University of Southampton, University Road, Southampton, SO17 1BJ, UK.
³ Department of Pharmacy, University of Patras, 26504, Patras, Greece.
⁴ School of Physics, University College Dublin (UCD), Belfield, Dublin, 4, Ireland.
⁵ Cátedra de Química Inorgánica, Departamento Estrella Campos, Facultadde Química, Universidad de la República, Avda. General Flores 2124, CC 1157, Montevideo, Uruguay.
⁶ Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann von Helmholtz Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.

Abstract

We have added the {Re^IV X₅ }^- (X=Br, Cl) synthon to a pocket-based ligand to provide supramolecular design using halogen⋅⋅⋅halogen interactions within an Fe^III system that has the potential to undergo spin crossover (SCO). By removing the solvent from the crystal lattice, we "switch on" halogen⋅⋅⋅halogen interactions between neighboring molecules, providing a supramolecular cooperative pathway for SCO. Furthermore, changes to the halogen-based interaction allow us to modify the temperature and nature of the SCO event.

Keywords: cooperative effects; halogen bonding; noncovalent interactions; self-assembly; spin crossover.

Abstract

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