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Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane
Author(s) -
Brummel Olaf,
Besold Daniel,
Döpper Tibor,
Wu Yanlin,
Bochmann Sebastian,
Lazzari Federica,
Waidhas Fabian,
Bauer Udo,
Bachmann Philipp,
Papp Christian,
Steinrück HansPeter,
Görling Andreas,
Libuda Jörg,
Bachmann Julien
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201600127
Subject(s) - quadricyclane , norbornadiene , density functional theory , oxidizing agent , chemistry , molecule , electrochemistry , photochemistry , redox , computational chemistry , electrode , catalysis , inorganic chemistry , organic chemistry
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.