Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane
Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane
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DOI：
10.1002/cssc.201600127
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发表时间：
2016-06-22
期刊：
影响因子：
8.4
通讯作者：
Bachmann, Julien
中科院分区：
文献类型：
--
作者：
Brummel, Olaf;Besold, Daniel;Bachmann, Julien
我们研究了电化学触发的四环烷 (QC) 环化转化为降冰片二烯 (NBD)，该系统具有将能量存储和转换结合在单个分子中的潜力。纯 NBD 和纯 QC 获得了明确的伏安曲线，后者是前者的应变多环异构体。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着的能量差异，正如密度泛函理论 (DFT) 计算所证明的那样。每种纯化合物的振动模式在指纹区域中通过实验进行表征，并通过 DFT 方法进行识别。通过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。 QC 环回至 NBD 的动力学由氧化当量催化，可以通过施加的电极电势进行控制，这意味着能够实时调整 QC 中存储的热能的释放。
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 insitu 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.