Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane

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• 作者：Olaf Brummel ; Daniel Besold ; Tibor Dö ; pper ; Yanlin Wu ; Sebastian Bochmann ; Federica Lazzari ; Fabian Waidhas ; Udo Bauer ; Philipp Bachmann ; Dr. Christian Papp ; Prof. Hans-Peter Steinrü ; ck ; Prof. Andreas Gö ; rling ; Prof. Jö ; rg Libuda and Prof. Julien Bachmann
• 刊名：ChemSusChem
• 出版年：2016
• 出版时间：June 22, 2016
• 年：2016
• 卷：9
• 期：12
• 页码：1424-1432
• 全文大小：1749K
• ISSN：1864-564X

文摘

We have investigated the electrochemically triggered cycloreversion of quadricyclane (QC) to norbornadiene (NBD), a system that holds the potential to combine both energy storage and conversion in a single molecule. Unambiguous voltammetric traces are obtained for pure NBD and pure QC, the latter a strained polycyclic isomer of the former. The difference in redox potentials is smaller than the energy difference between the neutral molecules. This is owing to a significant energy difference between the corresponding radical cations, as demonstrated by density functional theory (DFT) calculations. The vibrational modes of each pure compound are characterized experimentally in the fingerprint region and identified by DFT methods. Thermal and electrochemical transformations of NBD and QC are monitored in situ by IR spectroelectrochemical methods. The kinetics of the cycloreversion of QC to NBD, which is catalyzed by oxidizing equivalents, can be controlled by an applied electrode potential, which implies the ability to adjust in real time the release of thermal power stored in QC.