Please use this identifier to cite or link to this item: https://hdl.handle.net/10316/107459
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dc.contributor.authorPinheiro, Daniela-
dc.contributor.authorGalvão, Adelino-
dc.contributor.authorPineiro, Marta-
dc.contributor.authorMelo, J. Sérgio Seixas de-
dc.date.accessioned2023-07-13T09:13:45Z-
dc.date.available2023-07-13T09:13:45Z-
dc.date.issued2021-04-29-
dc.identifier.issn1520-6106pt
dc.identifier.issn1520-5207pt
dc.identifier.urihttps://hdl.handle.net/10316/107459-
dc.description.abstractIn 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.sponsorshipThis 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.isoengpt
dc.publisherACS American Chemical Societypt
dc.relationProject “Hylight” (no. 031625) 02/SAICT/2017pt
dc.relationinfo:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC/QUI-QFI/31625/2017/PT/Rational Design of High Efficiency and Stability Organic-Inorganic Hybrid White Light Emitterspt
dc.relationProject Suprasol/LISBOA-01-0145-FEDERpt
dc.relationinfo:eu-repo/grantAgreement/FCT/9471 - RIDTI/PTDC/QUI-QOR/28365/2017/PT/Supramolecular assemblies for efficient, stable, and sustainable organic solar cellspt
dc.relationPOCI-01-0145-FEDER- 016387/Project SunStorage - Harvesting and storage of solar energypt
dc.relationUIDB/00313/2020pt
dc.relationUIDP/00313/2020pt
dc.relationUID/QUI/00100/2019pt
dc.relationinfo: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 Applicationpt
dc.rightsembargoedAccesspt
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/pt
dc.titleRed-Purple Photochromic Indigos from Green Chemistry: Mono-tBOC or Di-tBOC N-Substituted Indigos Displaying Excited State Proton Transfer or Photoisomerizationpt
dc.typearticle-
degois.publication.firstPage4108pt
degois.publication.lastPage4119pt
degois.publication.issue16pt
degois.publication.titleThe Journal of Physical Chemistry Bpt
dc.peerreviewedyespt
dc.identifier.doi10.1021/acs.jpcb.1c00120pt
degois.publication.volume125pt
dc.date.embargo2022-04-29*
uc.date.periodoEmbargo365pt
item.fulltextCom Texto completo-
item.cerifentitytypePublications-
item.languageiso639-1en-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.grantfulltextopen-
item.openairetypearticle-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0001-5897-6020-
crisitem.author.orcid0000-0002-7460-3758-
crisitem.author.orcid0000-0001-9708-5079-
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais
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