Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization
We investigated the influence of triisopropylsilyl (TIPS) functionalization on annihilators in triplet–triplet annihilation photon upconversion, specifically focusing on their spin statistical probability factor. A new green-emitting annihilator 3,9-bis((triisopropylsilyl)ethynyl)perylene (TIPS-PY)...
| Autores: | , , , , , , , , , , , , , , |
|---|---|
| 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:2117/450996 |
| Acceso en línea: | https://hdl.handle.net/2117/450996 https://dx.doi.org/10.1039/d5sc05248c |
| Access Level: | acceso abierto |
| Palabra clave: | Chemical engineering Enginyeria química Àrees temàtiques de la UPC::Enginyeria química |
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Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalizationNaimovicius, LukasDapkevicius, ManvydasRadiunas, EdvinasMiroshnichenko, MilaKreiza, GediminasAlcaide, Carles|||0000-0002-0611-870XBaronas, Paulius|||0000-0002-4141-1485Sasaki, YoichiYanai, Nobuhiro|||0000-0003-0297-6544Kimizuka, NobuoPun, Andrew B.|||0000-0002-3052-912XSolà, MiquelBharmoria, Pankaj|||0000-0001-6573-0475Kazlauskas, KarolisMoth-Poulsen, Kasper|||0000-0003-4018-4927Chemical engineeringEnginyeria químicaÀrees temàtiques de la UPC::Enginyeria químicaWe investigated the influence of triisopropylsilyl (TIPS) functionalization on annihilators in triplet–triplet annihilation photon upconversion, specifically focusing on their spin statistical probability factor. A new green-emitting annihilator 3,9-bis((triisopropylsilyl)ethynyl)perylene (TIPS-PY) displaying a record red-to-green TTA-UC quantum yield of 13.7% (50% theoretical maximum) was synthesized. This remarkable efficiency was achieved due to the following features of the TIPS functionalization of PY: (1) retaining a high fluorescence quantum yield of 95%, (2) reduced triplet energy to 1.29 eV enabling efficient triplet energy transfer (~100%) from the sensitizer PdTPBP (T1 = 1.55 eV), and (3) a high efficiency of singlet generation after triplet coupling, indicated by the statistical probability factor, f = 39.2% ± 2.4%. Notably, the f value of TIPS-PY surpasses other annihilators in the 470–570 nm emission range. Excited state computational analysis using TheoDORE revealed a higher percentage of charge transfer character in S0S1 in TIPS-PY compared to PY, indicative of higher singlet-like character in their triplet-pair state 1(T1T1), which can enhance the coupling of the triplet-pair state with the excited singlet-state, thereby increasing the efficiency of singlet generation, a phenomenon undisclosed before. Furthermore, the suitable T1 of TIPS-PY enables upconversion of 730 nm light when sensitized with Os(m-peptpy)2(TFSI)2 (T1 = 1.63 eV), demonstrating the broad upconversion range of TIPS-PY in the phototherapeutic window desired for biological applications.Peer ReviewedRoyal Society of Chemistry (RSC)20252025-11-2120262026-01-22journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/2117/450996https://dx.doi.org/10.1039/d5sc05248creponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)Inglésengopen 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:2117/4509962026-05-27T15:37:01Z |
| dc.title.none.fl_str_mv |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| title |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| spellingShingle |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization Naimovicius, Lukas Chemical engineering Enginyeria química Àrees temàtiques de la UPC::Enginyeria química |
| title_short |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| title_full |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| title_fullStr |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| title_full_unstemmed |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| title_sort |
Enhancing the statistical probability factor in triplet–triplet annihilation photon upconversion via TIPS functionalization |
| dc.creator.none.fl_str_mv |
Naimovicius, Lukas Dapkevicius, Manvydas Radiunas, Edvinas Miroshnichenko, Mila Kreiza, Gediminas Alcaide, Carles|||0000-0002-0611-870X Baronas, Paulius|||0000-0002-4141-1485 Sasaki, Yoichi Yanai, Nobuhiro|||0000-0003-0297-6544 Kimizuka, Nobuo Pun, Andrew B.|||0000-0002-3052-912X Solà, Miquel Bharmoria, Pankaj|||0000-0001-6573-0475 Kazlauskas, Karolis Moth-Poulsen, Kasper|||0000-0003-4018-4927 |
| author |
Naimovicius, Lukas |
| author_facet |
Naimovicius, Lukas Dapkevicius, Manvydas Radiunas, Edvinas Miroshnichenko, Mila Kreiza, Gediminas Alcaide, Carles|||0000-0002-0611-870X Baronas, Paulius|||0000-0002-4141-1485 Sasaki, Yoichi Yanai, Nobuhiro|||0000-0003-0297-6544 Kimizuka, Nobuo Pun, Andrew B.|||0000-0002-3052-912X Solà, Miquel Bharmoria, Pankaj|||0000-0001-6573-0475 Kazlauskas, Karolis Moth-Poulsen, Kasper|||0000-0003-4018-4927 |
| author_role |
author |
| author2 |
Dapkevicius, Manvydas Radiunas, Edvinas Miroshnichenko, Mila Kreiza, Gediminas Alcaide, Carles|||0000-0002-0611-870X Baronas, Paulius|||0000-0002-4141-1485 Sasaki, Yoichi Yanai, Nobuhiro|||0000-0003-0297-6544 Kimizuka, Nobuo Pun, Andrew B.|||0000-0002-3052-912X Solà, Miquel Bharmoria, Pankaj|||0000-0001-6573-0475 Kazlauskas, Karolis Moth-Poulsen, Kasper|||0000-0003-4018-4927 |
| author2_role |
author author author author author author author author author author author author author author |
| dc.subject.none.fl_str_mv |
Chemical engineering Enginyeria química Àrees temàtiques de la UPC::Enginyeria química |
| topic |
Chemical engineering Enginyeria química Àrees temàtiques de la UPC::Enginyeria química |
| description |
We investigated the influence of triisopropylsilyl (TIPS) functionalization on annihilators in triplet–triplet annihilation photon upconversion, specifically focusing on their spin statistical probability factor. A new green-emitting annihilator 3,9-bis((triisopropylsilyl)ethynyl)perylene (TIPS-PY) displaying a record red-to-green TTA-UC quantum yield of 13.7% (50% theoretical maximum) was synthesized. This remarkable efficiency was achieved due to the following features of the TIPS functionalization of PY: (1) retaining a high fluorescence quantum yield of 95%, (2) reduced triplet energy to 1.29 eV enabling efficient triplet energy transfer (~100%) from the sensitizer PdTPBP (T1 = 1.55 eV), and (3) a high efficiency of singlet generation after triplet coupling, indicated by the statistical probability factor, f = 39.2% ± 2.4%. Notably, the f value of TIPS-PY surpasses other annihilators in the 470–570 nm emission range. Excited state computational analysis using TheoDORE revealed a higher percentage of charge transfer character in S0S1 in TIPS-PY compared to PY, indicative of higher singlet-like character in their triplet-pair state 1(T1T1), which can enhance the coupling of the triplet-pair state with the excited singlet-state, thereby increasing the efficiency of singlet generation, a phenomenon undisclosed before. Furthermore, the suitable T1 of TIPS-PY enables upconversion of 730 nm light when sensitized with Os(m-peptpy)2(TFSI)2 (T1 = 1.63 eV), demonstrating the broad upconversion range of TIPS-PY in the phototherapeutic window desired for biological applications. |
| publishDate |
2025 |
| dc.date.none.fl_str_mv |
2025 2025-11-21 2026 2026-01-22 |
| 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/2117/450996 https://dx.doi.org/10.1039/d5sc05248c |
| url |
https://hdl.handle.net/2117/450996 https://dx.doi.org/10.1039/d5sc05248c |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| 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 |
Royal Society of Chemistry (RSC) |
| publisher.none.fl_str_mv |
Royal Society of Chemistry (RSC) |
| dc.source.none.fl_str_mv |
reponame:UPCommons. Portal del coneixement obert de la UPC instname:Universitat Politècnica de Catalunya (UPC) |
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Universitat Politècnica de Catalunya (UPC) |
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UPCommons. Portal del coneixement obert de la UPC |
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UPCommons. Portal del coneixement obert de la UPC |
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1869405096058552320 |
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15,812455 |