Conformational Spin Switching and Spin‐Selective Hydrogenation of a Magnetically Bistable Carbene. (27th August 2019)

• Record Type: Journal Article
• Authors: Trosien, Iris; Mendez‐Vega, Enrique; Thomanek, Tobias; Sander, Wolfram
• Is Part Of: Angewandte Chemie. Volume 131:Number 42(2019)
• Page Start: 14997
• Page End: 15001
• Publication Date: 2019-08-27
• Subjects: Carbene -- Hydrierung -- Konformation -- Matrix-Isolation -- Spin-Crossover; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201906579
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The control of the spin states of molecules opens the path to tuning selectivity in chemical reactions and to developing novel magnetically switchable materials. 3‐Methoxy‐9‐fluorenylidene is a carbene that is generated in cryogenic matrices both in its lowest energy singlet and triplet states, and the ratio of these states can be shifted by selective irradiation. The interconversion of the nearly degenerate spin states is induced by a conformational change of the methoxy group: switching the methoxy group into the "up" position results in the singlet state and switching into the "down" position in the triplet state. The spin control via a remote functional group makes this carbene unique for the study of spin‐specific reactions, which is demonstrated for the hydrogenation reaction. Spin switching by switching the conformation of a remote functional group is a novel phenomenon with potential applications in the design of functional materials. Abstract : Schaltbar : Der Spin‐Zustand (Singulett oder Triplett) eines magnetisch bistabilen Carbens wird von einer entfernten Methoxygruppe als Konformationsschalter gesteuert. Diese konformative Spinumschaltung kann verwendet werden, um die Spinabhängigkeit von Reaktionen zu untersuchen und hat potenzielle Anwendungen bei der Entwicklung neuartiger schaltbarer magnetischer Materialien.