Research output: Contribution to journal › Article › peer-review
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; Laptenkova, Anastasia V.; Selyutin, Artem A.; Bogachev, Nikita A.; Skripkin, Mikhail Yu; Ryazantsev, Mikhail N.; Tkachenko, Nikolai; Mereshchenko, Andrey S.
In: Journal of Physical Chemistry B, Vol. 124, No. 18, 07.05.2020, p. 3724-3733.Research output: Contribution to journal › Article › peer-review
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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 - 2020/5/7
Y1 - 2020/5/7
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.
KW - TRANSIENT ABSORPTION-SPECTROSCOPY
KW - EXCITED-STATE
KW - DYNAMICS
KW - RELAXATION
KW - SPECTRA
KW - CHROMIUM(3)
UR - http://www.scopus.com/inward/record.url?scp=85084379376&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.0c00088
DO - 10.1021/acs.jpcb.0c00088
M3 - Article
C2 - 32283018
AN - SCOPUS:85084379376
VL - 124
SP - 3724
EP - 3733
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 18
ER -
ID: 60312120