Journal ArticleDOI
Substituted Diarylnorbornadienes and Quadricyclanes: Synthesis, Photochemical Properties, and Effect of Substituent on the Kinetic Stability of Quadricyclanes.
Kyle J. Spivack,Jesse V. Walker,Maria J. Sanford,Benjamin R. Rupert,Andrew R. Ehle,James M. Tocyloski,Aaron N. Jahn,Lyndsey M. Shaak,Obiamaka Obianyo,Karyn M. Usher,Felix E. Goodson +10 more
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TLDR
It is determined that the reversion of the quadricyclanes occurs via a free radical mechanism with very little contribution from polar effects, and speculation is speculated as to whether this data may form the basis for a freeradical substituent constant, σQ•, analogous to the traditional Hammett σ parameter.Abstract:
In this Article, we present a new method for the synthesis of diarylnorbornadiene derivatives. Through the use of a two-step procedure consisting of a tandem alkene insertion-Suzuki coupling reaction followed by a DDQ dehydrogenation, we have been able to synthesize derivatives with a wide variety of substituents. We also present the results of UV–visible spectroscopy studies and kinetics experiments that show the effect of substituent on light absorption properties of the norbornadienes as well as the kinetic stability of the quadricyclanes that result from their photochemical conversion. While substitution on the aromatic rings had comparatively little effect on quadricyclane lability, substitution at a bridgehead position with a methyl group produced a quadricyclane that thermally reverted to the norbornadiene at a rate that was significantly slower than that for the quadricyclane without the methyl substituent. From the results of the kinetics experiments, we determined that the reversion of the quadr...read more
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Journal ArticleDOI
Liquid Norbornadiene Photoswitches for Solar Energy Storage
Ambra Dreos,Zhihang Wang,Jonas Udmark,Anna Ström,Paul Erhart,Karl Börjesson,Mogens Brøndsted Nielsen,Kasper Moth-Poulsen +7 more
TL;DR: In this article, a set of neat liquid norbornadiene derivatives for MOST applications and their characterization in toluene solutions and neat samples are presented, showing that they can absorb up to 10% of the solar spectrum with a measured energy storage density of up to 577 kJ/kg corresponding to 152 kJ mol−1(calculated 100 kJmol−1).
Journal ArticleDOI
Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications
TL;DR: The most impactful recent findings on how to engineer key properties of the NBD/QC system (photochemistry, energy storage, heat release, stability, and synthesis) are described as well as examples of test devices for solar energy capture and heat release.
Journal ArticleDOI
Unraveling factors leading to efficient norbornadiene–quadricyclane molecular solar-thermal energy storage systems
Kjell Jorner,Ambra Dreos,Rikard Emanuelsson,Ouissam El Bakouri,Ignacio Fernández Galván,Karl Börjesson,Karl Börjesson,Ferran Feixas,Roland Lindh,Burkhard Zietz,Kasper Moth-Poulsen,Henrik Ottosson +11 more
TL;DR: In this article, a series of norbornadiene-quadricyclane (NBD-R2) doubly substituted at the C7-position with R = H, Me, and iPr was studied.
Journal ArticleDOI
Probing the Delicate Balance between Pauli Repulsion and London Dispersion with Triphenylmethyl Derivatives
TL;DR: It is concluded that the most important factor for HPE stability arises from LD interactions, and large, rigid, and symmetric hydrocarbon moieties act as excellent dispersion energy donors.
Journal ArticleDOI
Solvent Effects on the Absorption Profile, Kinetic Stability, and Photoisomerization Process of the Norbornadiene–Quadricyclanes System
TL;DR: In this article, solvent effects on photowitches based on the norbornadiene-quadricyclane (NBD-QC) couple were explored for the first time.
References
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Journal ArticleDOI
A survey of Hammett substituent constants and resonance and field parameters
Corwin Hansch,A. Leo,R. W. Taft +2 more
TL;DR: The Hammett equation has been widely used for the study and interpretation of organic reactions and their mechanisms as mentioned in this paper, and it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution.
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"Aromatic" substituent constants for structure-activity correlations
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Chemical solutions for the closed-cycle storage of solar energy
TL;DR: In this paper, a review analyzes the inherent scientific challenges of realizing the potential of storing solar energy by photochemical generation of high-energy metastable compounds whose subsequent thermal isomerization releases large amounts of low-temperature (<500 K) heat.