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

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• 作者：Jovana Milić ; Michal Zalibera ; Igor Pochorovski ; Nils Trapp ; Julia Nomrowski ; Dmytro Neshchadin ; Laurent Ruhlmann ; Corinne Boudon ; Oliver S. Wenger ; Anton Savitsky ; Wolfgang Lubitz ; Georg Gescheidt ; François Diederich
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：July 7, 2016
• 年：2016
• 卷：7
• 期：13
• 页码：2470-2477
• 全文大小：555K
• 年卷期：0
• ISSN：1948-7185

文摘

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.