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 language | English (US) |
---|---|
Pages (from-to) | 17670-17680 |
Number of pages | 11 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 41 |
DOIs | |
State | Published - Oct 14 2020 |
Externally published | Yes |
Bibliographical note
Publisher Copyright:© 2020 American Chemical Society.