Application of surface-enhanced resonance Raman scattering (SERS) to the study of organic functional materials: electronic structure and charge transfer properties of 9,10-bis((<i>E</i>)-2-(pyridin-4-yl)vinyl)anthracene

Soto, Juan; Imbarack, Elizabeth; López‐Tocón, Isabel; Sánchez-Cortés, Santiago; Otero, Juan C.; Leyton, Patricio

doi:10.1039/c9ra01269a

Cited by 20 publications

(25 citation statements)

References 55 publications

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“…The optimized structures ( Figure S1) and the respective force fields of isolated bpyvn and the Ag 2 -bpyvn complex in their respective ground electronic states (S 0 ) were carried out at the same CAM-B3LYP/def2-TZVPP level of theory previously used in a related system [7]. A neutral silver dimer attached to bpyvn through one of its nitrogen atoms was selected as a model of the surface complex near the potential of zero charge of a rough silver electrode which would lie in the range −0.5 V to −0.8 V [32].…”

Section: Electronic Structure Of Bpyvn and Ag 2 -Bpyvn Complexmentioning

confidence: 99%

“…Then, their respective electronic structures, that is, the vertical energy of the first ten excited electronic states at the Franck-Condon point (S i = 1-10 ) were calculated by using the time-dependent DFT method at the same level of computation. This type of calculation has already been successfully employed in a previous work to predict the electronic structure of a related molecule [7].…”

Section: Dft Calculationsmentioning

confidence: 99%

“…Different conformers of bpyvn can be optimized, depending on the relative position of the pyridine planes with respect to the naphthalene one. We chose the most stable structure by rotating both aromatic rings with respect to the naphthalene [7]. Two silver atoms linked to the molecule through one of the nitrogen atom were added to optimize the Ag 2 -bpyvn complex.…”

Section: Dft Calculationsmentioning

confidence: 99%

“…Resonance Raman spectra of bpyvn and Ag 2 -bpyvn complex were calculated according to a modified vibronic theory of Albrecht [40,41], in which only Franck-Condon factors are taken into account. Details of the calculations of the resonance Raman intensities have been given previously [7,[48][49][50][51][52]. Briefly, the method follows the independent mode displaced harmonic oscillator (IMDHO) approach where small displacements of the excited state with respect to the ground state geometry are considered to be proportional to the gradient (forces) on the excited state potential energy surface.…”

Section: Computational Resonance Raman Spectramentioning

confidence: 99%

“…The chemical enhancement mechanism, in turn, can contain different contributions: (1) the effect of the adsorption of the molecule on the metal [6], which modifies the molecular properties in its electronic ground state, and/or (2) the presence of resonant Raman processes up to (2a) excited electronic states of the own adsorbate (surface-enhanced resonance Raman scattering (SERRS) [7] similar to resonance Raman of the molecule) or (2b) to new metal-to-molecule charge transfer states of the surface complex (SERS-CT) [8][9][10][11], where an electron is transferred in the transient excited state. While the metal plays the main role in the electromagnetic mechanism, the chemical contributions are very dependent on the particular molecular system and the experimental conditions.…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2019

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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 Ag2-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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Section: Electronic Structure Of Bpyvn and Ag 2 -Bpyvn Complexmentioning

confidence: 99%

Section: Dft Calculationsmentioning

confidence: 99%

Section: Dft Calculationsmentioning

confidence: 99%

Section: Computational Resonance Raman Spectramentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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

et al. 2019

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Spiroconjugated Tetraaminospirenes as Donors in Color‐Tunable Charge‐Transfer Emitters with Donor‐Acceptor Structure

Grenz

Rose

Wössner

et al. 2021

Chemistry A European J

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Charge-transfer emitters are attractive due to their color tunability and potentially high photoluminescence quantum yields (PLQYs). We herein present tetraaminospirenes as donor moieties, which, in combination with a variety of acceptors, furnished 12 charge-transfer emitters with a range of emission colors and PLQYs of up to 99 %. The spatial separation of their frontier molecular orbitals was obtained through careful structural design, and two DA structures were confirmed by X-ray crystallography. A range of photophysical measurements supported by DFT calculations shed light on the optoelectronic properties of this new family of spiro-NNdonor-acceptor dyes.

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Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations

Algarra

Soto

2020

ChemPhysChem

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This work studies the photochemical and thermal decompositions of azidoacetonitrile (N3CH2CN) from both the experimental and theoretical points of view. The data of the photochemical experiments are taken from the literature, while the thermal decomposition have been carried out by us. In addition, we have performed ab initio calculations of the multiconfigurational type [complete active space self‐consistent field (CASSCF) and the multistate multireference perturbation theory (MS‐CASPT2)]. It is found that the first step of both type of decompositions is N2 elimination and formation of closed shell singlet nitrene. Afterwards, the nitrene tends to rapidly rearrange into formimidoyl cyanide (HNCHCN). As both reactions progress, the imine isomerizes into formimidoyl isocyanide (HNCHNC). The photoisomerization of the imine takes places thorough a conical intersection, while the same reaction on the ground electronic state occurs via a conventional transition state. The last step of the global reaction is decomposition of the imines into HCN and CNH. In photochemical conditions, the conjunction of the imines and its dissociation products (HCN and CNH) yields adenine

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Application of surface-enhanced resonance Raman scattering (SERS) to the study of organic functional materials: electronic structure and charge transfer properties of 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene

Abstract: Surface enhanced Raman spectroscopy in conjunction with quantum chemistry is a valuable tool for characterization of organic functional materials.

Cited by 20 publications

References 55 publications

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

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

Spiroconjugated Tetraaminospirenes as Donors in Color‐Tunable Charge‐Transfer Emitters with Donor‐Acceptor Structure

Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations

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