Reversible Switching of Organic Diradical Character via Iron-Based Spin-Crossover

Airi Kawamura, Jiaze Xie, Jan Niklas Boyn, Kate A. Jesse, Andrew J. McNeece, Ethan A. Hill, Kelsey A. Collins, Juan A. Valdez-Moreira, Alexander S. Filatov, Josh W. Kurutz, David A. Mazziotti, John S. Anderson

Research output: Contribution to journalArticlepeer-review

33 Scopus citations

Abstract

Organic diradicals are uncommon species that have been intensely studied for their unique properties and potential applicability in a diverse range of innovative fields. While there is a growing class of stable and well-characterized organic diradicals, there has been recent focus on how diradical character can be controlled or modulated with external stimuli. Here we demonstrate that a diiron complex bridged by the doubly oxidized ligand tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFtt2-) undergoes a thermally induced Fe-centered spin-crossover which yields significant diradical character on TTFtt2-. UV-vis-near-IR, Mössbauer, NMR, and EPR spectroscopies with magnetometry, crystallography, and advanced theoretical treatments suggest that this diradical character arises from a shrinking TTFtt2- π-manifold from the Fe(II)-centered spin-crossover. The TTFtt2-centered diradical is predicted to have a singlet ground state by theory and variable temperature EPR. This unusual phenomenon demonstrates that inorganic spin transitions can be used to modulate organic diradical character.

Original languageEnglish (US)
Pages (from-to)17670-17680
Number of pages11
JournalJournal of the American Chemical Society
Volume142
Issue number41
DOIs
StatePublished - Oct 14 2020
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2020 American Chemical Society.

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