A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

Danielle Cristina Teles-Ferreira, Irene Conti, Rocío Borrego-Varillas, Artur Nenov, Ivo H.M. Van Stokkum, Lucia Ganzer, Cristian Manzoni, Ana Maria de Paula, Giulio Cerullo, Marco Garavelli

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub-20 fs broadband transient absorption spectroscopy in the near-UV are combined with CASPT2/MM decay path calculations to unravel the excited-state decay channels of water solvated 2-thio and 2,4-dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4-dithiouracil decay pathways is shown to be strongly correlated either to those of 2- or 4-thiouracil, depending on the sulfur atom on which the electronic transition localizes.

Original languageEnglish
Pages (from-to)336-343
Number of pages8
JournalChemistry - A European Journal
Volume26
Issue number1
Early online date21 Nov 2019
DOIs
Publication statusPublished - 2 Jan 2020

Fingerprint

Uracil
Absorption spectroscopy
Excited states
Absorption spectra
Sulfur
Thiouracil
Derivatives
Atoms
Aquaporins
Molecules
Water
2,4-dithiouracil
4-thiouracil

Keywords

  • CASPT2
  • conical intersections
  • QM/MM
  • thiobases
  • transient absorption
  • ultrafast spectroscopy

Cite this

Teles-Ferreira, Danielle Cristina ; Conti, Irene ; Borrego-Varillas, Rocío ; Nenov, Artur ; Van Stokkum, Ivo H.M. ; Ganzer, Lucia ; Manzoni, Cristian ; de Paula, Ana Maria ; Cerullo, Giulio ; Garavelli, Marco. / A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils. In: Chemistry - A European Journal. 2020 ; Vol. 26, No. 1. pp. 336-343.
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Teles-Ferreira, DC, Conti, I, Borrego-Varillas, R, Nenov, A, Van Stokkum, IHM, Ganzer, L, Manzoni, C, de Paula, AM, Cerullo, G & Garavelli, M 2020, 'A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils' Chemistry - A European Journal, vol. 26, no. 1, pp. 336-343. https://doi.org/10.1002/chem.201904541

A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils. / Teles-Ferreira, Danielle Cristina; Conti, Irene; Borrego-Varillas, Rocío; Nenov, Artur; Van Stokkum, Ivo H.M.; Ganzer, Lucia; Manzoni, Cristian; de Paula, Ana Maria; Cerullo, Giulio; Garavelli, Marco.

In: Chemistry - A European Journal, Vol. 26, No. 1, 02.01.2020, p. 336-343.

Research output: Contribution to JournalArticleAcademicpeer-review

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