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...

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Authors: Salthouse, Rebeca Jane|||0000-0003-2213-6956, Elholm, Jacob Lynge, Cortellazzi, Irene, Hölzel, Helen, Ferreira, Pedro Miguel Mendonça, Fernandez, Lorette Sylvie Jacqueline|||0000-0002-6776-7359, Hetherington, Jack, Moth-Poulsen, Kasper|||0000-0003-4018-4927
Format: article
Publication Date:2025
Country:España
Institution:Universitat Politècnica de Catalunya (UPC)
Repository:UPCommons. Portal del coneixement obert de la UPC
Language:English
OAI Identifier:oai:upcommons.upc.edu:2117/450683
Online Access:https://hdl.handle.net/2117/450683
https://dx.doi.org/10.1002/anie.202516629
Access Level:Open access
Keyword: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
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network_acronym_str ES
network_name_str España
repository_id_str
spelling Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimersSalthouse, Rebeca Jane|||0000-0003-2213-6956Elholm, Jacob LyngeCortellazzi, IreneHölzel, HelenFerreira, Pedro Miguel MendonçaFernandez, Lorette Sylvie Jacqueline|||0000-0002-6776-7359Hetherington, JackMoth-Poulsen, Kasper|||0000-0003-4018-4927FluorescenceNorbornadiene–quadricyclanePhotoswitchesSolar energy storageThermal energy releasÀrees temàtiques de la UPC::Enginyeria química::Química física::Estructura molecularÀrees temàtiques de la UPC::Enginyeria química::Química física::TermoquímicaÀrees temàtiques de la UPC::Enginyeria química::Química física::CinèticaÀrees temàtiques de la UPC::Enginyeria química::Química orgànica::Compostos orgànicsThe 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.The authors acknowledge funding from the European Commission's Horizon 2020 Framework Program under grant agreement number 951801 (H2020-EIC-FETPROACT-2019), the European Research Council under grant number 101002131 (CoG, PHOTHERM), the Swedish Research Council (vetenskapsrådet (2020-00686), the Spanish Research Council, PID2021-123873NB100 LIPCES and the European Innovation Council (EIC) under the project ESiM (grant agreement No. 101046364). We thank Laura Duncan (Durham University) for running mass spectrometry samples and Maria del Barrio (UPC) for the DSC measurements.Peer ReviewedJohn Wiley & sons20252025-11-0420262026-01-16journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/2117/450683https://dx.doi.org/10.1002/anie.202516629reponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)InglésengAgencia Estatal de Investigación http://doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2021-123873NB-I00 LUZ COMO INDUCTOR DE CAMBIO DE FASE PARA ALMACENAMIENTO DE ENERGIA EN SISTEMAS DE MATERIALES SUPRAMOLECULARESopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:upcommons.upc.edu:2117/4506832026-05-27T15:37:01Z
dc.title.none.fl_str_mv Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
title Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
spellingShingle Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
Salthouse, Rebeca Jane|||0000-0003-2213-6956
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
title_short Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
title_full Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
title_fullStr Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
title_full_unstemmed Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
title_sort Modulation of photoluminescence and solar thermal energy storage in norbornadiene–quadricyclane dimers
dc.creator.none.fl_str_mv Salthouse, Rebeca Jane|||0000-0003-2213-6956
Elholm, Jacob Lynge
Cortellazzi, Irene
Hölzel, Helen
Ferreira, Pedro Miguel Mendonça
Fernandez, Lorette Sylvie Jacqueline|||0000-0002-6776-7359
Hetherington, Jack
Moth-Poulsen, Kasper|||0000-0003-4018-4927
author Salthouse, Rebeca Jane|||0000-0003-2213-6956
author_facet Salthouse, Rebeca Jane|||0000-0003-2213-6956
Elholm, Jacob Lynge
Cortellazzi, Irene
Hölzel, Helen
Ferreira, Pedro Miguel Mendonça
Fernandez, Lorette Sylvie Jacqueline|||0000-0002-6776-7359
Hetherington, Jack
Moth-Poulsen, Kasper|||0000-0003-4018-4927
author_role author
author2 Elholm, Jacob Lynge
Cortellazzi, Irene
Hölzel, Helen
Ferreira, Pedro Miguel Mendonça
Fernandez, Lorette Sylvie Jacqueline|||0000-0002-6776-7359
Hetherington, Jack
Moth-Poulsen, Kasper|||0000-0003-4018-4927
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv 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
topic 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
description 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.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-11-04
2026
2026-01-16
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/2117/450683
https://dx.doi.org/10.1002/anie.202516629
url https://hdl.handle.net/2117/450683
https://dx.doi.org/10.1002/anie.202516629
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2021-123873NB-I00 LUZ COMO INDUCTOR DE CAMBIO DE FASE PARA ALMACENAMIENTO DE ENERGIA EN SISTEMAS DE MATERIALES SUPRAMOLECULARES
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv John Wiley & sons
publisher.none.fl_str_mv John Wiley & sons
dc.source.none.fl_str_mv reponame:UPCommons. Portal del coneixement obert de la UPC
instname:Universitat Politècnica de Catalunya (UPC)
instname_str Universitat Politècnica de Catalunya (UPC)
reponame_str UPCommons. Portal del coneixement obert de la UPC
collection UPCommons. Portal del coneixement obert de la UPC
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869425227214094336
score 15,811543

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