Structural dynamics of nitrosylruthenium isomeric complexes studied with steady-state and transient pump-probe infrared spectroscopies

Zhao, Yan; Yang, Fan; Wang, Jianru; Yu, Pengyun; Pan, Hongda; Wang, Hongfei; Wang, Jianping

doi:10.1016/j.saa.2016.04.055

Cited by 1 publication

(3 citation statements)

References 40 publications

(49 reference statements)

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“…The relaxation of nitrosyl ligand was studied in other complex such as sodium nitroprussside, with a relaxation time of 39 ps in DMSO and 23.8 ps in D 2 O, which are much slower than what we observed in the Ru-NO complex. However, the speedup of the vibrational relaxation time was also found in other nitrosyl complexes with ligand environment similar to our case, − i.e., the organic ligands, that were not present in earlier studied nitrosyl-containing systems. This indicates that the lifetime of the NO stretching excited state may be case dependent.…”

Section: Resultssupporting

confidence: 87%

“…33 cm −1 when solvent changes from dDMSO (1841.2 cm −1 ) to D 2 O (1874.2 cm −1 ). The NO absorption peak in dDMSO is fairly close to what was observed in a similar compound ([Ru(OAc)(2mqn) 2 NO] (H2mqn = 2methyl-8-quinolinol), 35 1845.7 cm −1 ) measured in KBr pallet (data not shown). This implies that in dDMSO the solute− solvent interaction is weak.…”

Section: Resultssupporting

confidence: 81%

“…In our recent works, − a similar Ru-NO complex with cis and trans configurations has been examined using ultrafast IR spectroscopies. It was found that nonlinear IR signatures (spectral line width, dynamical parameters), especially those extracted from 2D IR spectra, can be used to differentiate the cis and trans configurations .…”

Section: Introductionmentioning

confidence: 99%

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Linear and Nonlinear Infrared Spectroscopies Reveal Detailed Solute–Solvent Dynamic Interactions of a Nitrosyl Ruthenium Complex in Solution

Feng

Zhao

et al. 2018

J. Phys. Chem. B

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In this work, the solvation of a nitrosyl ruthenium complex, [(CH)N][RuCl(qn)(NO)] (with qn = deprotonated 8-hydroxyquinoline), which is a potential NO-releasing molecule in the bio-environment, was studied in two bio-friendly solvents, namely deuterated dimethyl sulfoxide (dDMSO) and water (DO). A blue-shifted NO stretching frequency was observed in water with respect to that in dDMSO, which was believed to be due to ligand-solvent hydrogen-bonding interactions, one N═O···D and particularly three Ru-Cl···D, that show competing effects on the NO bond length. The dynamic differences of the NO stretch in these two solvents were further revealed by transient pump-probe IR and two-dimensional IR results: faster vibrational relaxation and faster spectral diffusion (SD) were observed in DO, confirming stronger solvent-solute interaction and also faster solvent structural dynamics in DO than in DMSO. Further, a significant non-decaying residual in the SD dynamics was observed in DO but not in DMSO, suggesting the formation of a stable solvation shell in water due to strong multi-site ligand-solvent hydrogen-bonding interactions, which is in agreement with the observed blue-shifted NO stretching frequency. This work demonstrates that small solvent molecules such as water can form a relatively rigid solvation shell for certain transition metal complexes due to cooperative ligand-solvent interactions and show slower dynamics.

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