ArticleJournal of the American Chemical Society2026
Axially Chiral Bifluorenylidene Radical Anions with Long Spin-Lattice Relaxation Times at Room Temperature in Fluid Solution.
Article in Journal of the American Chemical Society, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Despite the recent interest in magnetochiral phenomena, well-characterized radicals that possess both molecular chirality and spin remain scarce. Herein, we report the synthesis of a series of axially chiral bifluorenylidene (BF) molecules and their singly reduced radical anions with varying degrees of fjord-region benzannulation. Our systematic structural perturbations provide insight into how the twist angle across their central C═C bond influences their redox state, electronic structure, stereochemical dynamics, and spin properties. Variable-temperature nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) studies are used to explore the barriers to major racemization processes. UV-vis-NIR absorption and magnetic circular dichroism spectroscopies provide insight into the electronic structures of the systems and are combined with multireference computational techniques to characterize the potential energy surfaces. Pulsed EPR measurements revealed that the BF radical anions displayed notably long spin-lattice (
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