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Title: An excited state dynamics driven reaction: wavelength-dependent photoisomerization quantum yields in [Ru(bpy)2(dmso)2]2+

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/d0sc00551g· OSTI ID:1671098
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States); Ohio Univ., Athens, OH (United States)
  2. Ohio Univ., Athens, OH (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
  4. Univ. Würzburg (Germany)
+ Show Author Affiliations

We report the excited-state behavior of a structurally simple bis-sulfoxide complex, cis-S,S-[Ru(bpy)2(dmso)2]2+, as investigated by femtosecond pump–probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis-S,O-[Ru(bpy)2(dmso)2]2+ and cis-O,O-[Ru(bpy)2(dmso)2]2+. The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis-O,O-[Ru(bpy)2(dmso)2]2+. Transient absorption measurements on cis-O,O-[Ru(bpy)2(dmso)2]2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump–repump–probe transient absorption spectroscopy of cis-S,S-[Ru(bpy)2(dmso)2]2+ shows that a pump–repump time delay of 3 ps dramatically alters the S,O:O,O product ratio; pump–repump–probe transient absorption spectroscopy of cis-O,O-[Ru(bpy)2(dmso)2]2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
Grant/Contract Number:
89233218CNA000001; CHE 1602240; CHE 1856492
OSTI ID:
1671098
Report Number(s):
LA-UR-20-22521
Journal Information:
Chemical Science, Vol. 11, Issue 22; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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