Influence of the N atom position on the excited state photodynamics of protonated azaindole

Noble, J. A.; Marceca, Ernesto; Dedonder, Claude; Phasayavan, Witchaya; Féraud, Géraldine; Inceesungvorn, Burapat; Jouvet, Christophe

doi:10.1039/d0cp03608k

Cited by 12 publications

(25 citation statements)

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“…The hypothesis that Dewar structures play a role in the S3 lifetime of 6-and 7-AIH + had already been raised in Ref. 25 . However, in that paper, the discussion focused on Dewar bonds between atoms 4 and 7, while here, we see them between atoms 5 and 7a.…”

Section: S3 Lifetimesmentioning

confidence: 99%

“…This out-of-plane minimum is in good agreement with the experiment, which exhibits a low-frequency vibrational progression in S3 assigned to out-ofplane modes. 25 The rings in the S1 and S2 minima are planar with the H atom attached with the six-membered ring N atom is marginally out of the plane.…”

Section: Topography and Dynamicsmentioning

confidence: 99%

“…Experimental spectral width and derived lifetimes of n-AIH + isomers from Ref. 25 Although one can find a handful of articles on 7-azaindole in isolated monomer, [5][6][7][8] in dimeric forms 5,[9][10][11][12][13] and water and alcohol clusters, 11,[14][15][16][17][18][19][20] only one recent article 21 to date shed light upon the photophysical relaxation mechanism of n-azaindole molecules by studying gasphase excited-state dynamics. Experiments and theoretical calculations have also been devoted 16,18,[22][23][24] to understanding the excited-state proton transfer and tautomerization mechanism of 7-azaindole with solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

“…Experiments and theoretical calculations have also been devoted 16,18,[22][23][24] to understanding the excited-state proton transfer and tautomerization mechanism of 7-azaindole with solvent molecules. On the other hand, very recently, Noble et al performed 25 photo-fragmentation spectroscopy on the protonated n-azaindole isomers (n-AIH + , n = 5, 6, 7) to explore the role of the n-nitrogen atom position on photodynamics. From the spectral line widths, they estimated the excited-state lifetimes ( )…”

Section: Introductionmentioning

confidence: 99%

“…parameters of the S3 population curves of 6-and 7-AIH + for simulations at ADC(2)/aug-cc-pVDZ. Experimental lifetimes from ref 25. are shown in parenthesis.…”

mentioning

confidence: 99%

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Weak Dewar bond modulates protonated azaindole photodynamics

Mansour

Mukherjee

Pinheiro

et al. 2022

Preprint

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Recent experimental work revealed that the lifetime of the S3 state of protonated 7-azaindole is about ten times slower than that of protonated 6-azaindole. We simulated the nonradiative decay pathways of these molecules using trajectory surface hopping dynamics after photoexcitation into S3 to elucidate the reason for this difference. Both isomers mainly follow a common pp* relaxation pathway involving multiple state crossings while coming down from S3 to S1 in the subpicosecond time scale. However, the simulations reveal that the excited-state topographies are such that while the 6-isomer can easily access the region of nonadiabatic transitions, the internal conversion of the 7-isomer is delayed by a pre-Dewar bond formation with a boat conformation.

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Section: S3 Lifetimesmentioning

confidence: 99%

Section: Topography and Dynamicsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…parameters of the S3 population curves of 6-and 7-AIH + for simulations at ADC(2)/aug-cc-pVDZ. Experimental lifetimes from ref 25. are shown in parenthesis.…”

mentioning

confidence: 99%

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Weak Dewar bond modulates protonated azaindole photodynamics

Mansour

Mukherjee

Pinheiro

et al. 2022

Preprint

Self Cite

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Gas phase electronic spectra of xylene-water aggregates

Fulker

Gutiérrez-Quintanilla

Brown

et al. 2023

Journal of Molecular Spectroscopy

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Linking Electronic Relaxation Dynamics and Ionic Photofragmentation Patterns for the Deprotonated UV Filter Benzophenone-4

Wong

Rankine

Dessent

2021

J. Phys. Chem. Lett.

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Understanding how deprotonation impacts the photophysics of UV filters is critical to better characterize how they behave in key alkaline environments including surface waters and coral reefs. Using anion photodissociation spectroscopy, we have measured the intrinsic absorption electronic spectroscopy (400–214 nm) and numerous accompanying ionic photofragmentation pathways of the benzophenone-4 anion ([BP4–H] − ). Relative ion yield plots reveal the locations of the bright S 1 and S 3 excited states. For the first time for an ionic UV filter, ab initio potential energy surfaces are presented to provide new insight into how the photofragment identity maps the relaxation pathways. These calculations reveal that [BP4–H] − undergoes excited-state decay consistent with a statistical fragmentation process where the anion breaks down on the ground state after nonradiative relaxation. The broader relevance of the results in providing a basis for interpreting the relaxation dynamics of a wide range of gas-phase ionic systems is discussed.

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Influence of the N atom position on the excited state photodynamics of protonated azaindole

Abstract: Competition between relaxation pathways from S1 and S3 in protonated n-azaindole.

Cited by 12 publications

References 49 publications

Weak Dewar bond modulates protonated azaindole photodynamics

Weak Dewar bond modulates protonated azaindole photodynamics

Gas phase electronic spectra of xylene-water aggregates

Linking Electronic Relaxation Dynamics and Ionic Photofragmentation Patterns for the Deprotonated UV Filter Benzophenone-4

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