Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/107459
DC Field | Value | Language |
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dc.contributor.author | Pinheiro, Daniela | - |
dc.contributor.author | Galvão, Adelino | - |
dc.contributor.author | Pineiro, Marta | - |
dc.contributor.author | Melo, J. Sérgio Seixas de | - |
dc.date.accessioned | 2023-07-13T09:13:45Z | - |
dc.date.available | 2023-07-13T09:13:45Z | - |
dc.date.issued | 2021-04-29 | - |
dc.identifier.issn | 1520-6106 | pt |
dc.identifier.issn | 1520-5207 | pt |
dc.identifier.uri | https://hdl.handle.net/10316/107459 | - |
dc.description.abstract | In indigo, excited state proton transfer (ESPT) is known to be associated with the molecular mechanism responsible for highly efficient radiationless deactivation. When this route is blocked (partially or totally), new deactivation routes become available. Using new green chemistry procedures, with favorable green chemistry metrics, monosubstitution and disubstitution of N group(s) in indigo, by tert-butoxy carbonyl groups, N-(tert-butoxycarbonyl)indigo (NtBOCInd) and N,N'-(tert-butoxycarbonyl)indigo (N,N'tBOCInd), respectively, were synthetically accomplished. The compounds display red to purple colors depending on the solvent and substitution. Different excited-state deactivation pathways were observed and found to be structure- and solvent-dependent. Trans-cis photoisomerization was found to be absent with NtBOCInd and present with N,N'tBOCInd in nonpolar solvents. Time-resolved fluorescence experiments revealed single-exponential decays for the two compounds which, linked to time-dependent density functional theory (TDDFT) studies, show that with NtBOCInd ESPT is extremely fast and barrierless-predicted to be 1 kJ mol-1 in methylcyclohexane and 5 kJ mol-1 in dimethylsulfoxide-, which contrasts with ∼11 kJ mol-1 experimentally obtained for indigo. An alternative ESPT, competitive with the N-H···O═C intramolecular pathway, involving dimer units is also probed by TDDFT and found to be consistent with the experimentally observed time-resolved data. N,N'tBOCInd, where ESPT is precluded, shows solvent-dependent trans-cis/cis-trans photoisomerization and is surprisingly found to be more stable in the nonemissive cis conformation, whose deactivation to S0 is found to be solvent-dependent. | pt |
dc.description.sponsorship | This work was supported by Project “Hylight” (no. 031625) 02/SAICT/2017, PTDC/QUI-QFI/31625/2017, which is funded by the Portuguese Science Foundation and Compete Centro 2020, Project Suprasol (LISBOA-01-0145-FEDER- 028365 − PTDC/QUI-QOR/28365/2017), funded by Fundo Europeu de Desenvolvimento Regional (FEDER), through Programa Operacional Regional LISBOA (LISBOA2020), financially supported by project “SunStorage - Harvesting and storage of solar energy” reference POCI-01-0145-FEDER- 016387, funded by FEDER, through Programa Operacional Factores de Competitividade (COMPETE) 2020 - Operational Programme for Competitiveness and Internationalization (OPCI), and by national funds, through Fundação para a Ciência e a Tecnologia (FCT), the Portuguese Agency for Scientific Research. We also acknowledge funding by FEDER through COMPETE. The Coimbra Chemistry Centre is supported by the FCT, through Projects UIDB/00313/2020 and UIDP/00313/2020, and CQE is supported by the FCT through project UID/QUI/00100/2019. The FCT is also gratefully acknowledged for a PhD grant to D. Pinheiro (ref SFRH/BD/74351/2010). D. Pinheiro also acknowledges the project “SunStorage - Harvesting and storage of solar energy” for a research grant. | pt |
dc.language.iso | eng | pt |
dc.publisher | ACS American Chemical Society | pt |
dc.relation | Project “Hylight” (no. 031625) 02/SAICT/2017 | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC/QUI-QFI/31625/2017/PT/Rational Design of High Efficiency and Stability Organic-Inorganic Hybrid White Light Emitters | pt |
dc.relation | Project Suprasol/LISBOA-01-0145-FEDER | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC/QUI-QOR/28365/2017/PT/Supramolecular assemblies for efficient, stable, and sustainable organic solar cells | pt |
dc.relation | POCI-01-0145-FEDER- 016387/Project SunStorage - Harvesting and storage of solar energy | pt |
dc.relation | UIDB/00313/2020 | pt |
dc.relation | UIDP/00313/2020 | pt |
dc.relation | UID/QUI/00100/2019 | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/FARH/SFRH/BD/74351/2010/PT/alterado para: Synthesis and Photophysical Exploration of New Chemosensors. Synthesis and Photophysical Exploration of New Bio-Inspired Chemosensors with Excimer/Exciplex Formation: In Vitro Application | pt |
dc.rights | embargoedAccess | pt |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | pt |
dc.title | Red-Purple Photochromic Indigos from Green Chemistry: Mono-tBOC or Di-tBOC N-Substituted Indigos Displaying Excited State Proton Transfer or Photoisomerization | pt |
dc.type | article | - |
degois.publication.firstPage | 4108 | pt |
degois.publication.lastPage | 4119 | pt |
degois.publication.issue | 16 | pt |
degois.publication.title | The Journal of Physical Chemistry B | pt |
dc.peerreviewed | yes | pt |
dc.identifier.doi | 10.1021/acs.jpcb.1c00120 | pt |
degois.publication.volume | 125 | pt |
dc.date.embargo | 2022-04-29 | * |
uc.date.periodoEmbargo | 365 | pt |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.grantfulltext | open | - |
item.openairetype | article | - |
item.languageiso639-1 | en | - |
item.fulltext | Com Texto completo | - |
item.cerifentitytype | Publications | - |
crisitem.project.grantno | Coimbra Chemistry Center | - |
crisitem.project.grantno | Coimbra Chemistry Center | - |
crisitem.author.researchunit | CQC - Coimbra Chemistry Centre | - |
crisitem.author.researchunit | CQC - Coimbra Chemistry Centre | - |
crisitem.author.researchunit | CQC - Coimbra Chemistry Centre | - |
crisitem.author.parentresearchunit | Faculty of Sciences and Technology | - |
crisitem.author.parentresearchunit | Faculty of Sciences and Technology | - |
crisitem.author.parentresearchunit | Faculty of Sciences and Technology | - |
crisitem.author.orcid | 0000-0001-5897-6020 | - |
crisitem.author.orcid | 0000-0002-7460-3758 | - |
crisitem.author.orcid | 0000-0001-9708-5079 | - |
Appears in Collections: | I&D CQC - Artigos em Revistas Internacionais |
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Red-Purple Photochromic Indigos from Green Chemistry Mono-tBOC or Di-tBOC N-Substituted Indigos Displaying Excited State Proton Transfer or Photoisomerization.pdf | 3.74 MB | Adobe PDF | View/Open |
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