Ultrafast Photochemistry of the [Cr(NCS)6]3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State

Taras A. Khvorost; Leonid Yu Beliaev; Ekaterina Potalueva; Anastasia V. Laptenkova; Artem A. Selyutin; Nikita A. Bogachev; Mikhail Yu Skripkin; Mikhail N. Ryazantsev; Nikolai Tkachenko; Andrey S. Mereshchenko

doi:10.1021/acs.jpcb.0c00088

Ultrafast Photochemistry of the [Cr(NCS)₆]^3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State

Taras A. Khvorost, Leonid Yu Beliaev, Ekaterina Potalueva, Anastasia V. Laptenkova, Artem A. Selyutin, Nikita A. Bogachev, Mikhail Yu Skripkin, Mikhail N. Ryazantsev, Nikolai Tkachenko, Andrey S. Mereshchenko

Materiaalitiede ja ympäristötekniikka

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

5 Sitaatiot (Scopus)

Abstrakti

The ultrafast photochemistry of the [Cr(NCS)₆]^3- complex upon excitation to the ⁴T₂ ligand-field (LF) state was studied in dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a wide temporal range (100 fs to 9 ms) by a combination of femtosecond and nanosecond transient absorption spectroscopy techniques and supported by quantum-chemical DFT/TD-DFT calculations. The initially excited ⁴T₂ state undergoes intersystem crossing to the vibrationally hot ²E state with time constants of 1.1 ± 0.2 and 1.8 ± 0.1 ps in DMSO and DMF, respectively. Vibrational relaxation occurs in the same time scale and takes 1-5 ps. A major part of the [Cr(NCS)₆]^3- complex in the ²E state undergoes intersystem crossing to the ground state with time constants of 65 ± 5 and 85 ± 5 ns in DMSO and DMF, respectively. A minor part of electronically excited [Cr(NCS)₆]^3- undergoes irreversible photochemical decomposition. In DMSO, the photolysis of the [Cr(NCS)₆]^3- complex results in single or double isothiocyanate ion release followed by the coordination of the solvent molecules with a time constant of 1 ± 0.2 ms.

Alkuperäiskieli	Englanti
Sivut	3724-3733
Sivumäärä	10
Julkaisu	Journal of Physical Chemistry B
Vuosikerta	124
Numero	18
DOI - pysyväislinkit	https://doi.org/10.1021/acs.jpcb.0c00088
Tila	Julkaistu - 2020
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

The measurements were performed in the Research Park of Saint-Petersburg State University (“Magnetic Resonance Research Centre”, “SPbU Computing Centre”, “Cryogenic Department”, “Interdisciplinary Resource Centre for Nanotechnology”, “Centre for X-ray Diffraction Studies”, and “Centre for Optical and Laser Materials Research”) and in Faculty of Engineering and Natural Sciences of Tampere University. The reported study was funded by RFBR, project number 20-33-70025.

Julkaisufoorumi-taso

Jufo-taso 1

!!ASJC Scopus subject areas

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

Pääsy asiakirjaan

10.1021/acs.jpcb.0c00088

Siteeraa tätä

Khvorost, T. A., Beliaev, L. Y., Potalueva, E., Laptenkova, A. V., Selyutin, A. A., Bogachev, N. A., Skripkin, M. Y., Ryazantsev, M. N., Tkachenko, N., & Mereshchenko, A. S. (2020). Ultrafast Photochemistry of the [Cr(NCS)₆]^3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State. Journal of Physical Chemistry B, 124(18), 3724-3733. https://doi.org/10.1021/acs.jpcb.0c00088

@article{e701a65f83de42dfbb8ec8637b08eb7c,

title = "Ultrafast Photochemistry of the [Cr(NCS)6]3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State",

abstract = "The ultrafast photochemistry of the [Cr(NCS)6]3- complex upon excitation to the 4T2 ligand-field (LF) state was studied in dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a wide temporal range (100 fs to 9 ms) by a combination of femtosecond and nanosecond transient absorption spectroscopy techniques and supported by quantum-chemical DFT/TD-DFT calculations. The initially excited 4T2 state undergoes intersystem crossing to the vibrationally hot 2E state with time constants of 1.1 ± 0.2 and 1.8 ± 0.1 ps in DMSO and DMF, respectively. Vibrational relaxation occurs in the same time scale and takes 1-5 ps. A major part of the [Cr(NCS)6]3- complex in the 2E state undergoes intersystem crossing to the ground state with time constants of 65 ± 5 and 85 ± 5 ns in DMSO and DMF, respectively. A minor part of electronically excited [Cr(NCS)6]3- undergoes irreversible photochemical decomposition. In DMSO, the photolysis of the [Cr(NCS)6]3- complex results in single or double isothiocyanate ion release followed by the coordination of the solvent molecules with a time constant of 1 ± 0.2 ms.",

author = "Khvorost, {Taras A.} and Beliaev, {Leonid Yu} and Ekaterina Potalueva and Laptenkova, {Anastasia V.} and Selyutin, {Artem A.} and Bogachev, {Nikita A.} and Skripkin, {Mikhail Yu} and Ryazantsev, {Mikhail N.} and Nikolai Tkachenko and Mereshchenko, {Andrey S.}",

year = "2020",

doi = "10.1021/acs.jpcb.0c00088",

language = "English",

volume = "124",

pages = "3724--3733",

journal = "Journal of Physical Chemistry B",

issn = "1520-6106",

publisher = "American Chemical Society",

number = "18",

}

Khvorost, TA, Beliaev, LY, Potalueva, E, Laptenkova, AV, Selyutin, AA, Bogachev, NA, Skripkin, MY, Ryazantsev, MN, Tkachenko, N & Mereshchenko, AS 2020, 'Ultrafast Photochemistry of the [Cr(NCS)₆]^3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State', Journal of Physical Chemistry B, Vuosikerta 124, Nro 18, Sivut 3724-3733. https://doi.org/10.1021/acs.jpcb.0c00088

Ultrafast Photochemistry of the [Cr(NCS)₆]^3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State. / Khvorost, Taras A.; Beliaev, Leonid Yu; Potalueva, Ekaterina et al.
julkaisussa: Journal of Physical Chemistry B, Vuosikerta 124, Nro 18, 2020, s. 3724-3733.

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

TY - JOUR

T1 - Ultrafast Photochemistry of the [Cr(NCS)6]3- Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State

AU - Khvorost, Taras A.

AU - Beliaev, Leonid Yu

AU - Potalueva, Ekaterina

AU - Laptenkova, Anastasia V.

AU - Selyutin, Artem A.

AU - Bogachev, Nikita A.

AU - Skripkin, Mikhail Yu

AU - Ryazantsev, Mikhail N.

AU - Tkachenko, Nikolai

AU - Mereshchenko, Andrey S.

PY - 2020

Y1 - 2020

N2 - The ultrafast photochemistry of the [Cr(NCS)6]3- complex upon excitation to the 4T2 ligand-field (LF) state was studied in dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a wide temporal range (100 fs to 9 ms) by a combination of femtosecond and nanosecond transient absorption spectroscopy techniques and supported by quantum-chemical DFT/TD-DFT calculations. The initially excited 4T2 state undergoes intersystem crossing to the vibrationally hot 2E state with time constants of 1.1 ± 0.2 and 1.8 ± 0.1 ps in DMSO and DMF, respectively. Vibrational relaxation occurs in the same time scale and takes 1-5 ps. A major part of the [Cr(NCS)6]3- complex in the 2E state undergoes intersystem crossing to the ground state with time constants of 65 ± 5 and 85 ± 5 ns in DMSO and DMF, respectively. A minor part of electronically excited [Cr(NCS)6]3- undergoes irreversible photochemical decomposition. In DMSO, the photolysis of the [Cr(NCS)6]3- complex results in single or double isothiocyanate ion release followed by the coordination of the solvent molecules with a time constant of 1 ± 0.2 ms.

AB - The ultrafast photochemistry of the [Cr(NCS)6]3- complex upon excitation to the 4T2 ligand-field (LF) state was studied in dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a wide temporal range (100 fs to 9 ms) by a combination of femtosecond and nanosecond transient absorption spectroscopy techniques and supported by quantum-chemical DFT/TD-DFT calculations. The initially excited 4T2 state undergoes intersystem crossing to the vibrationally hot 2E state with time constants of 1.1 ± 0.2 and 1.8 ± 0.1 ps in DMSO and DMF, respectively. Vibrational relaxation occurs in the same time scale and takes 1-5 ps. A major part of the [Cr(NCS)6]3- complex in the 2E state undergoes intersystem crossing to the ground state with time constants of 65 ± 5 and 85 ± 5 ns in DMSO and DMF, respectively. A minor part of electronically excited [Cr(NCS)6]3- undergoes irreversible photochemical decomposition. In DMSO, the photolysis of the [Cr(NCS)6]3- complex results in single or double isothiocyanate ion release followed by the coordination of the solvent molecules with a time constant of 1 ± 0.2 ms.

U2 - 10.1021/acs.jpcb.0c00088

DO - 10.1021/acs.jpcb.0c00088

M3 - Article

C2 - 32283018

AN - SCOPUS:85084379376

SN - 1520-6106

VL - 124

SP - 3724

EP - 3733

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 18

ER -