Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study
Replacement of a phenyl moiety by a carborane in 1,3-di(4-carboxyphenyl) derivatives has a pronounced effect on the photophysical properties of the compounds themselves and their corresponding Eu3+ and Tb3+ metal organic frameworks. Herein, we demonstrate that while the luminescence of the carborane...
| Autores: | , , , , , , |
|---|---|
| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2024 |
| País: | España |
| Recursos: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositório: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/346033 |
| Acesso em linha: | http://hdl.handle.net/10261/346033 https://api.elsevier.com/content/abstract/scopus_id/85182873308 |
| Access Level: | Acceso aberto |
| Palavra-chave: | O-carborane Energy transfer Boron Photoluminescence |
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Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| title |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| spellingShingle |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study Li, Zhen O-carborane Energy transfer Boron Photoluminescence |
| title_short |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| title_full |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| title_fullStr |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| title_full_unstemmed |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| title_sort |
Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational study |
| dc.creator.none.fl_str_mv |
Li, Zhen Roscini, Claudio Núñez Aguilera, Rosario Teixidor, Francesc Viñas, Clara Ruiz, Eliseo Giner Planas, José |
| author |
Li, Zhen |
| author_facet |
Li, Zhen Roscini, Claudio Núñez Aguilera, Rosario Teixidor, Francesc Viñas, Clara Ruiz, Eliseo Giner Planas, José |
| author_role |
author |
| author2 |
Roscini, Claudio Núñez Aguilera, Rosario Teixidor, Francesc Viñas, Clara Ruiz, Eliseo Giner Planas, José |
| author2_role |
author author author author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Ciencia, Innovación y Universidades (España) Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) Generalitat de Catalunya China Scholarship Council Dezhou University European Commission Roscini, Claudio [0000-0002-0157-8934] Núñez Aguilera, Rosario [0000-0003-4582-5148] Teixidor, Francesc [0000-0002-3010-2417] Viñas, Clara [0000-0001-5000-0277] Ruiz, Eliseo [0000-0001-9097-8499] Giner Planas, José [0000-0002-1648-2169] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
O-carborane Energy transfer Boron Photoluminescence |
| topic |
O-carborane Energy transfer Boron Photoluminescence |
| description |
Replacement of a phenyl moiety by a carborane in 1,3-di(4-carboxyphenyl) derivatives has a pronounced effect on the photophysical properties of the compounds themselves and their corresponding Eu3+ and Tb3+ metal organic frameworks. Herein, we demonstrate that while the luminescence of the carborane-derivative 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane (mCB-L) is negligible in the solid state (0.3%), the corresponding phenyl-derivative [1,1′ : 3′,1′′-terphenyl]-4,4′′-dicarboxylic] (TDCA) is highly luminescent (quantum yield of 47.8%). However, the latter one is a much worse antenna for sensitizing Eu3+ and Tb3+ cations than the former one. Based on our previous studies where mCB-L behaves as a good antenna for these two lanthanides, we have now comparatively studied the optical properties of mCB-L and TDCA and their efficiency as sensitizers for Eu and Tb cations, in the solid state at room temperature. STEOM-DLPNO-CCSD calculations revealed a larger energy difference between the singlet S1 and the lowest conical intersection (CI) points for TDCA (33.0 kcal mol−1) than that for mCB-L (18.4 kcal mol−1), explaining the observed different luminescence properties of these two compounds. Contrary to the carborane derivative, TDCA exhibits a more distorted structure at the CI point. TDCA-Eu and TDCA-Tb MOFs have been synthesized and characterized by infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). The optical properties of TDCA-Eu and TDCA-Tb MOFs were investigated, and both MOFs displayed luminescence in the visible region with characteristic emission bands attributed to Eu3+ and Tb3+ transitions, respectively. However, the quantum yields for TDCA-Ln (Eu, 11.1%; Tb, 4.8%) were found to be much lower than those of carborane-based MOFs (Eu, 20.5%; Tb, 49.8%), indicating that the TDCA ligand is a less efficient light-absorbing sensitizer for Eu3+ and Tb3+ ions compared to the carborane-based ligand and may favor undesired back-energy transfer, as suggested by their faster decay times in comparison with the carborane counterparts. STEOM-DLPNO-CCSD calculations are used to analyze the changes in electron densities on photo-excitation from S0 to S1 and de-excitation from T1 to S0, as well as the differences in the excited state energies for mCB-L, TDCA, and the hypothetical longer derivatives (mCB-L2 and QDCA). Our research, which combines experimental and computational methods, offers valuable data for optimizing the singlet and triplet energies, as well as their differences (gaps), by choosing between phenyl and carborane as the building scaffold for 1,3-di(4-carboxyphenyl) compounds. This demonstrates that using phenyl or m-carborane as the building scaffold leads to distinct luminescence properties. |
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2024 |
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2024 2024 2024 |
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info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
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http://hdl.handle.net/10261/346033 https://api.elsevier.com/content/abstract/scopus_id/85182873308 |
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http://hdl.handle.net/10261/346033 https://api.elsevier.com/content/abstract/scopus_id/85182873308 |
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Inglés |
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Inglés |
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Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu<sup>3+</sup> and Tb<sup>3+</sup> metal-organic frameworks: a combined experimental and computational studyLi, ZhenRoscini, ClaudioNúñez Aguilera, RosarioTeixidor, FrancescViñas, ClaraRuiz, EliseoGiner Planas, JoséO-carboraneEnergy transferBoronPhotoluminescenceReplacement of a phenyl moiety by a carborane in 1,3-di(4-carboxyphenyl) derivatives has a pronounced effect on the photophysical properties of the compounds themselves and their corresponding Eu3+ and Tb3+ metal organic frameworks. Herein, we demonstrate that while the luminescence of the carborane-derivative 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane (mCB-L) is negligible in the solid state (0.3%), the corresponding phenyl-derivative [1,1′ : 3′,1′′-terphenyl]-4,4′′-dicarboxylic] (TDCA) is highly luminescent (quantum yield of 47.8%). However, the latter one is a much worse antenna for sensitizing Eu3+ and Tb3+ cations than the former one. Based on our previous studies where mCB-L behaves as a good antenna for these two lanthanides, we have now comparatively studied the optical properties of mCB-L and TDCA and their efficiency as sensitizers for Eu and Tb cations, in the solid state at room temperature. STEOM-DLPNO-CCSD calculations revealed a larger energy difference between the singlet S1 and the lowest conical intersection (CI) points for TDCA (33.0 kcal mol−1) than that for mCB-L (18.4 kcal mol−1), explaining the observed different luminescence properties of these two compounds. Contrary to the carborane derivative, TDCA exhibits a more distorted structure at the CI point. TDCA-Eu and TDCA-Tb MOFs have been synthesized and characterized by infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). The optical properties of TDCA-Eu and TDCA-Tb MOFs were investigated, and both MOFs displayed luminescence in the visible region with characteristic emission bands attributed to Eu3+ and Tb3+ transitions, respectively. However, the quantum yields for TDCA-Ln (Eu, 11.1%; Tb, 4.8%) were found to be much lower than those of carborane-based MOFs (Eu, 20.5%; Tb, 49.8%), indicating that the TDCA ligand is a less efficient light-absorbing sensitizer for Eu3+ and Tb3+ ions compared to the carborane-based ligand and may favor undesired back-energy transfer, as suggested by their faster decay times in comparison with the carborane counterparts. STEOM-DLPNO-CCSD calculations are used to analyze the changes in electron densities on photo-excitation from S0 to S1 and de-excitation from T1 to S0, as well as the differences in the excited state energies for mCB-L, TDCA, and the hypothetical longer derivatives (mCB-L2 and QDCA). Our research, which combines experimental and computational methods, offers valuable data for optimizing the singlet and triplet energies, as well as their differences (gaps), by choosing between phenyl and carborane as the building scaffold for 1,3-di(4-carboxyphenyl) compounds. This demonstrates that using phenyl or m-carborane as the building scaffold leads to distinct luminescence properties.This work was financially supported by MICINN (PID2019-106832RB-I00, PID2021-122464NB-100, PID2022-136892NB-I00), and through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (EX2019-000917-S project), and by the Generalitat de Catalunya (2021/SGR/00286, 2021/SGR/00442). E. R. thanks Generalitat de Catalunya by an ICREA Academia award, Spanish Ministry Science for a Maria de Maeztu excellence grant (CEX2021-001202-M) and computer resources, technical expertise and assistance provided by the CSUC. Zhen Li acknowledges the China Scholarship Council (CSC) for his PhD grant (201808310071) and Scientific Research Foundation of Dezhou University (2023xjrc210). The present publication is dedicated to Prof. John D. Kennedy on the occasion of his 80th Birthday. Yin-yang symbol via Flickr (CC BY 2.0 licence).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2021-001202-M).Peer reviewedRoyal Society of Chemistry (UK)Ministerio de Ciencia, Innovación y Universidades (España)Ministerio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Generalitat de CatalunyaChina Scholarship CouncilDezhou UniversityEuropean CommissionRoscini, Claudio [0000-0002-0157-8934]Núñez Aguilera, Rosario [0000-0003-4582-5148]Teixidor, Francesc [0000-0002-3010-2417]Viñas, Clara [0000-0001-5000-0277]Ruiz, Eliseo [0000-0001-9097-8499]Giner Planas, José [0000-0002-1648-2169]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/346033https://api.elsevier.com/content/abstract/scopus_id/85182873308reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106832RB-I00info:eu-repo/grantAgreement/MICINN/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/PID2021-122464NB-100info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136892NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-Sinfo:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2021-001202-Minfo:eu-repo/grantAgreement/AEI//EX2019-000917-SJournal of Materials Chemistry CThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1039/D3TC04018Fhttp://doi.org/10.1039/d3tc04018fSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3460332026-05-22T06:33:51Z |
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15,812429 |