Synthesis, characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage
Research output: Contribution to journal › Journal article › Research › peer-review
Documents
- Fulltext
Final published version, 1.01 MB, PDF document
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.
Original language | English |
---|---|
Journal | Chemical Science |
Volume | 13 |
Issue number | 3 |
Pages (from-to) | 834–841 |
Number of pages | 8 |
ISSN | 2041-6520 |
DOIs | |
Publication status | Published - 2022 |
Number of downloads are based on statistics from Google Scholar and www.ku.dk
No data available
ID: 289165462