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Tytuł:
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Ultrafast Photochemistry of the [Cr(NCS) 6 ] Complex in Dimethyl Sulfoxide and Dimethylformamide upon Excitation into Ligand-Field Electronic State.
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Autorzy:
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Khvorost TA; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Beliaev LY; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Potalueva E; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Laptenkova AV; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Selyutin AA; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Bogachev NA; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Skripkin MY; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
Ryazantsev MN; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.; Saint Petersburg Academic University, ul. Khlopina 8/3, St. Petersburg, 194021, Russia.
Tkachenko N; Chemistry and Advanced Materials Group, Faculty of Engineering and Natural Sciences, Tampere University, Korkeakoulunkatu 8, FI-33720 Tampere, Finland.
Mereshchenko AS; Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russia.
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Źródło:
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The journal of physical chemistry. B [J Phys Chem B] 2020 May 07; Vol. 124 (18), pp. 3724-3733. Date of Electronic Publication: 2020 Apr 28.
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Typ publikacji:
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Journal Article; Research Support, Non-U.S. Gov't
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Język:
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English
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Imprint Name(s):
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Original Publication: Washington, D.C. : American Chemical Society, c1997-
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MeSH Terms:
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Dimethyl Sulfoxide*
Dimethylformamide*
Electronics ; Ligands ; Photochemistry
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Substance Nomenclature:
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0 (Ligands)
8696NH0Y2X (Dimethylformamide)
YOW8V9698H (Dimethyl Sulfoxide)
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Entry Date(s):
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Date Created: 20200414 Date Completed: 20210514 Latest Revision: 20210514
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Update Code:
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20240105
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DOI:
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10.1021/acs.jpcb.0c00088
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PMID:
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32283018
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The ultrafast photochemistry of the [Cr(NCS) 6 ] 3- complex upon excitation to the 4 T 2 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 4 T 2 state undergoes intersystem crossing to the vibrationally hot 2 E 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 2 E 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.
