Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
The norbornadiene/quadricyclane (NBD/QC) photoswitch pair is a promising system for molecular solar thermal (MOST) energy storage. Multichromophoric systems with two or more photoswitches can offer red-shifted absorption, higher energy densities, and additional functionality. Here, a series of ortho...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Universitat Politècnica de Catalunya (UPC) |
| Repositorio: | UPCommons. Portal del coneixement obert de la UPC |
| Idioma: | inglés |
| OAI Identifier: | oai:upcommons.upc.edu:2117/450683 |
| Acceso en línea: | https://hdl.handle.net/2117/450683 https://dx.doi.org/10.1002/anie.202516629 |
| Access Level: | acceso abierto |
| Palabra clave: | Fluorescence Norbornadiene–quadricyclane Photoswitches Solar energy storage Thermal energy releas Àrees temàtiques de la UPC::Enginyeria química::Química física::Estructura molecular Àrees temàtiques de la UPC::Enginyeria química::Química física::Termoquímica Àrees temàtiques de la UPC::Enginyeria química::Química física::Cinètica Àrees temàtiques de la UPC::Enginyeria química::Química orgànica::Compostos orgànics |
| Sumario: | The norbornadiene/quadricyclane (NBD/QC) photoswitch pair is a promising system for molecular solar thermal (MOST) energy storage. Multichromophoric systems with two or more photoswitches can offer red-shifted absorption, higher energy densities, and additional functionality. Here, a series of ortho- and para-substituted NBD dimers bearing methoxy, hexoxy (for solubility), and cyano groups were synthesised and evaluated for their MOST properties. Compared to monomers, the dimers display red-shifted absorption and improved solar spectrum match, with onsets between 448–488 nm, owing to their donor–acceptor design and extended conjugation. A key finding is the tunable relationship between molecular structure, photoluminescence and photoisomerisation: para-dimers exhibit efficient fluorescence, whilst ortho-dimers are superior photoswitches with quantum yields of isomerisation, Fi, up to 63%. Solvent choice further modulates behaviour; Fi is higher in acetonitrile, whereas fluorescence is more efficient in toluene. This interplay allows tailoring for specific functions. The best-performing photoswitches were studied in a liquid-chip device, achieving a record solar conversion efficiency of 2.9%. Catalytic back-conversion using cobalt phthalocyanine on carbon and macroscopic heat release experiments at 0.1 M yielded a 5.78 °C temperature increase. This first experimental macroscopic heat release of a dimeric system provides important insights into design challenges and opportunities for advancing multichromophoric systems towards MOST applications. |
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