Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1002/cphc.202000452 http://hdl.handle.net/11449/199203 |
Resumo: | A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds. |
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Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolinesabsorption spectraacidochromismdensity functional theorydual emissionfluorescencequinolinesA combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds.Laboratory of Organic Synthesis and Processes (LOSP) São Paulo State University (UNESP) Department of Chemistry School of SciencesIMDEA Nanociencia Ciudad Universitaria de Cantoblanco, C/ Faraday 9Xi'an Institute of Flexible Electronics Northwestern Polytechnical University Dongda Town, Dongxiang Street 1Department for Physical Chemistry Faculty of Chemistry University of Valencia, Avenida Dr. Moliner 50Laboratory of Organic Synthesis and Processes (LOSP) São Paulo State University (UNESP) Department of Chemistry School of SciencesUniversidade Estadual Paulista (Unesp)Ciudad Universitaria de CantoblancoNorthwestern Polytechnical University Dongda TownUniversity of Valenciados Santos, Giovanny Carvalho [UNESP]Roldao, Juan CarlosShi, JunqingMilián-Medina, Begoñada Silva-Filho, Luiz Carlos [UNESP]Gierschner, Johannes2020-12-12T01:33:30Z2020-12-12T01:33:30Z2020-01-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1002/cphc.202000452ChemPhysChem.1439-76411439-4235http://hdl.handle.net/11449/19920310.1002/cphc.2020004522-s2.0-85088929387Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengChemPhysCheminfo:eu-repo/semantics/openAccess2021-10-23T04:53:23Zoai:repositorio.unesp.br:11449/199203Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462021-10-23T04:53:23Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
title |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
spellingShingle |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines dos Santos, Giovanny Carvalho [UNESP] absorption spectra acidochromism density functional theory dual emission fluorescence quinolines |
title_short |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
title_full |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
title_fullStr |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
title_full_unstemmed |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
title_sort |
Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines |
author |
dos Santos, Giovanny Carvalho [UNESP] |
author_facet |
dos Santos, Giovanny Carvalho [UNESP] Roldao, Juan Carlos Shi, Junqing Milián-Medina, Begoña da Silva-Filho, Luiz Carlos [UNESP] Gierschner, Johannes |
author_role |
author |
author2 |
Roldao, Juan Carlos Shi, Junqing Milián-Medina, Begoña da Silva-Filho, Luiz Carlos [UNESP] Gierschner, Johannes |
author2_role |
author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) Ciudad Universitaria de Cantoblanco Northwestern Polytechnical University Dongda Town University of Valencia |
dc.contributor.author.fl_str_mv |
dos Santos, Giovanny Carvalho [UNESP] Roldao, Juan Carlos Shi, Junqing Milián-Medina, Begoña da Silva-Filho, Luiz Carlos [UNESP] Gierschner, Johannes |
dc.subject.por.fl_str_mv |
absorption spectra acidochromism density functional theory dual emission fluorescence quinolines |
topic |
absorption spectra acidochromism density functional theory dual emission fluorescence quinolines |
description |
A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-12-12T01:33:30Z 2020-12-12T01:33:30Z 2020-01-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1002/cphc.202000452 ChemPhysChem. 1439-7641 1439-4235 http://hdl.handle.net/11449/199203 10.1002/cphc.202000452 2-s2.0-85088929387 |
url |
http://dx.doi.org/10.1002/cphc.202000452 http://hdl.handle.net/11449/199203 |
identifier_str_mv |
ChemPhysChem. 1439-7641 1439-4235 10.1002/cphc.202000452 2-s2.0-85088929387 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
ChemPhysChem |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1799964863484657664 |