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Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene

Electrochemical surface-enhanced Raman scattering (SERS) of the cruciform system 1,4-bis((E)-2-(pyridin-4-yl)vinyl)naphthalene (bpyvn) was recorded on nanostructured silver surfaces at different electrode potentials by using excitation laser lines of 785 and 514.5 nm. SERS relative intensities were...

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Autores principales: López-Tocón, Isabel, Imbarack, Elizabeth, Soto, Juan, Sanchez-Cortes, Santiago, Leyton, Patricio, Otero, Juan Carlos
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6943491/
https://www.ncbi.nlm.nih.gov/pubmed/31861152
http://dx.doi.org/10.3390/molecules24244622
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author López-Tocón, Isabel
Imbarack, Elizabeth
Soto, Juan
Sanchez-Cortes, Santiago
Leyton, Patricio
Otero, Juan Carlos
author_facet López-Tocón, Isabel
Imbarack, Elizabeth
Soto, Juan
Sanchez-Cortes, Santiago
Leyton, Patricio
Otero, Juan Carlos
author_sort López-Tocón, Isabel
collection PubMed
description Electrochemical surface-enhanced Raman scattering (SERS) of the cruciform system 1,4-bis((E)-2-(pyridin-4-yl)vinyl)naphthalene (bpyvn) was recorded on nanostructured silver surfaces at different electrode potentials by using excitation laser lines of 785 and 514.5 nm. SERS relative intensities were analyzed on the basis of the resonance Raman vibronic theory with the help of DFT calculations. The comparison between the experimental and the computed resonance Raman spectra calculated for the first five electronic states of the Ag(2)-bpyvn surface complex model points out that the selective enhancement of the SERS band recorded at about 1600 cm(−1), under 785 nm excitation, is due to a resonant Raman process involving a photoexcited metal-to-molecule charge transfer state of the complex, while the enhancement of the 1570 cm(−1) band using 514.5 nm excitation is due to an intramolecular π→π* electronic transition localized in the naphthalenyl framework, resulting in a case of surface-enhanced resonance Raman spectrum (SERRS). Thus, the enhancement of the SERS bands of bpyvn is controlled by a general chemical enhancement mechanism in which different resonance processes of the overall electronic structure of the metal-molecule system are involved.
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spelling pubmed-69434912020-01-10 Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene López-Tocón, Isabel Imbarack, Elizabeth Soto, Juan Sanchez-Cortes, Santiago Leyton, Patricio Otero, Juan Carlos Molecules Article Electrochemical surface-enhanced Raman scattering (SERS) of the cruciform system 1,4-bis((E)-2-(pyridin-4-yl)vinyl)naphthalene (bpyvn) was recorded on nanostructured silver surfaces at different electrode potentials by using excitation laser lines of 785 and 514.5 nm. SERS relative intensities were analyzed on the basis of the resonance Raman vibronic theory with the help of DFT calculations. The comparison between the experimental and the computed resonance Raman spectra calculated for the first five electronic states of the Ag(2)-bpyvn surface complex model points out that the selective enhancement of the SERS band recorded at about 1600 cm(−1), under 785 nm excitation, is due to a resonant Raman process involving a photoexcited metal-to-molecule charge transfer state of the complex, while the enhancement of the 1570 cm(−1) band using 514.5 nm excitation is due to an intramolecular π→π* electronic transition localized in the naphthalenyl framework, resulting in a case of surface-enhanced resonance Raman spectrum (SERRS). Thus, the enhancement of the SERS bands of bpyvn is controlled by a general chemical enhancement mechanism in which different resonance processes of the overall electronic structure of the metal-molecule system are involved. MDPI 2019-12-17 /pmc/articles/PMC6943491/ /pubmed/31861152 http://dx.doi.org/10.3390/molecules24244622 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
López-Tocón, Isabel
Imbarack, Elizabeth
Soto, Juan
Sanchez-Cortes, Santiago
Leyton, Patricio
Otero, Juan Carlos
Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title_full Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title_fullStr Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title_full_unstemmed Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title_short Intramolecular and Metal-to-Molecule Charge Transfer Electronic Resonances in the Surface-Enhanced Raman Scattering of 1,4-Bis((E)-2-(pyridin-4-yl)vinyl)naphthalene
title_sort intramolecular and metal-to-molecule charge transfer electronic resonances in the surface-enhanced raman scattering of 1,4-bis((e)-2-(pyridin-4-yl)vinyl)naphthalene
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6943491/
https://www.ncbi.nlm.nih.gov/pubmed/31861152
http://dx.doi.org/10.3390/molecules24244622
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