Brummel Olaf, Besold Daniel, Döpper Tibor, Wu Yanlin, Bochmann Sebastian, Lazzari Federica, Waidhas Fabian, Bauer Udo, Bachmann Philipp, Papp Christian, Steinrück Hans-Peter, Görling Andreas, Libuda Jörg, Bachmann Julien
Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
Lehrstuhl für Anorganische und Allgemeine Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.
ChemSusChem. 2016 Jun 22;9(12):1424-32. doi: 10.1002/cssc.201600127. Epub 2016 Apr 20.
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.
我们研究了四环烷（QC）电化学引发的环化逆反应生成降冰片二烯（NBD），该体系有可能在单个分子中同时实现能量存储和转换。对于纯NBD和纯QC，获得了明确的伏安曲线，后者是前者的一种张力多环异构体。氧化还原电位的差异小于中性分子之间的能量差异。这是由于相应的自由基阳离子之间存在显著的能量差异，密度泛函理论（DFT）计算证明了这一点。通过实验在指纹区对每种纯化合物的振动模式进行了表征，并通过DFT方法进行了识别。采用红外光谱电化学方法原位监测NBD和QC的热转化和电化学转化。由氧化当量催化的QC环化逆反应生成NBD的动力学可以通过施加的电极电位来控制，这意味着能够实时调节存储在QC中的热能释放。
