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Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage

Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch...

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Autores principales: Quant, Maria, Hillers-Bendtsen, Andreas Erbs, Ghasemi, Shima, Erdelyi, Mate, Wang, Zhihang, Muhammad, Lidiya M., Kann, Nina, Mikkelsen, Kurt V., Moth-Poulsen, Kasper
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8768882/
https://www.ncbi.nlm.nih.gov/pubmed/35173948
http://dx.doi.org/10.1039/d1sc05791j
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author Quant, Maria
Hillers-Bendtsen, Andreas Erbs
Ghasemi, Shima
Erdelyi, Mate
Wang, Zhihang
Muhammad, Lidiya M.
Kann, Nina
Mikkelsen, Kurt V.
Moth-Poulsen, Kasper
author_facet Quant, Maria
Hillers-Bendtsen, Andreas Erbs
Ghasemi, Shima
Erdelyi, Mate
Wang, Zhihang
Muhammad, Lidiya M.
Kann, Nina
Mikkelsen, Kurt V.
Moth-Poulsen, Kasper
author_sort Quant, Maria
collection PubMed
description Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch system has not until now been evaluated for MOST application, due to the short half-life of the TCO form and limited available synthetic methods. The BOD system degrades at higher temperature via a retro-Diels–Alder reaction, which complicates the synthesis of the compounds. We here report a cross-coupling reaction strategy that enables an efficient synthesis of a series of 4 new BOD compounds. We show that the BODs were able to switch to the corresponding tetracyclooctanes (TCOs) in a reversible way and can be cycled 645 times with only 0.01% degradation. Half-lives of the TCOs were measured, and we illustrate how the half-life could be engineered from seconds to minutes by molecular structure design. A density functional theory (DFT) based modelling framework was developed to access absorption spectra, thermal half-lives, and storage energies which were calculated to be 143–153 kJ mol(−1) (0.47–0.51 MJ kg(−1)), up to 76% higher than for the corresponding norbornadiene. The combined computational and experimental findings provide a reliable way of designing future BOD/TCO systems with tailored properties.
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spelling pubmed-87688822022-02-15 Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage Quant, Maria Hillers-Bendtsen, Andreas Erbs Ghasemi, Shima Erdelyi, Mate Wang, Zhihang Muhammad, Lidiya M. Kann, Nina Mikkelsen, Kurt V. Moth-Poulsen, Kasper Chem Sci Chemistry Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch system has not until now been evaluated for MOST application, due to the short half-life of the TCO form and limited available synthetic methods. The BOD system degrades at higher temperature via a retro-Diels–Alder reaction, which complicates the synthesis of the compounds. We here report a cross-coupling reaction strategy that enables an efficient synthesis of a series of 4 new BOD compounds. We show that the BODs were able to switch to the corresponding tetracyclooctanes (TCOs) in a reversible way and can be cycled 645 times with only 0.01% degradation. Half-lives of the TCOs were measured, and we illustrate how the half-life could be engineered from seconds to minutes by molecular structure design. A density functional theory (DFT) based modelling framework was developed to access absorption spectra, thermal half-lives, and storage energies which were calculated to be 143–153 kJ mol(−1) (0.47–0.51 MJ kg(−1)), up to 76% higher than for the corresponding norbornadiene. The combined computational and experimental findings provide a reliable way of designing future BOD/TCO systems with tailored properties. The Royal Society of Chemistry 2021-12-21 /pmc/articles/PMC8768882/ /pubmed/35173948 http://dx.doi.org/10.1039/d1sc05791j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Quant, Maria
Hillers-Bendtsen, Andreas Erbs
Ghasemi, Shima
Erdelyi, Mate
Wang, Zhihang
Muhammad, Lidiya M.
Kann, Nina
Mikkelsen, Kurt V.
Moth-Poulsen, Kasper
Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title_full Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title_fullStr Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title_full_unstemmed Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title_short Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
title_sort synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8768882/
https://www.ncbi.nlm.nih.gov/pubmed/35173948
http://dx.doi.org/10.1039/d1sc05791j
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