Paramagnetic Molecular Grippers: The Elements of Six-State Redox Switches

Milic, Jovana and Zalibera, Michal and Pochorovski, Igor and Trapp, Nils and Nomrowski, Julia and Neshchadin, Dmytro and Ruhlmann, Laurent and Boudon, Corinne and Wenger, Oliver S. and Savitsky, Anton and Lubitz, Wolfgang and Gescheit, Georg and Diederich, François. (2016) Paramagnetic Molecular Grippers: The Elements of Six-State Redox Switches. Journal of Physical Chemistry Letters, 7 (13). pp. 2470-2477.

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Official URL: http://edoc.unibas.ch/52006/

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The development of semiquinone-based resorcin[4]arene cavitands expands the toolbox of switchable molecular grippers by introducing the first paramagnetic representatives. The semiquinone (SQ) states were generated electrochemically, chemically, and photochemically. We analyzed their electronic, conformational, and binding properties by cyclic voltammetry, ultraviolet/visible (UV/vis) spectroelectrochemistry, electron paramagnetic resonance (EPR) and transient absorption spectroscopy, in conjunction with density functional theory (DFT) calculations. The utility of UV/vis spectroelectrochemistry and EPR spectroscopy in evaluating the conformational features of resorcin[4]arene cavitands is demonstrated. Guest binding properties were found to be enhanced in the SQ state as compared to the quinone (Q) or the hydroquinone (HQ) states of the cavitands. Thus, these paramagnetic SQ intermediates open the way to six-state redox switches provided by two conformations (open and closed) in three redox states (Q, SQ, and HQ) possessing distinct binding ability. The switchable magnetic properties of these molecular grippers and their responsiveness to electrical stimuli has the potential for development of efficient molecular devices.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Nomrowski, Julia
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:07 Jul 2020 07:47
Deposited On:11 Jan 2017 15:11

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