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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...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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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. |
format | Online Article Text |
id | pubmed-8768882 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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