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Spectrochim Acta A Mol Biomol Spectrosc. 2016 Sep 5;166:62-67. doi: 10.1016/j.saa.2016.04.055. Epub 2016 May 7.

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

Author information

1
College of Physics & Electronics Engineering, Shanxi University, Taiyuan 030006, China; Molecular Reaction Dynamics Laboratory, Beijing National Laboratory for Molecular Sciences, Beijing 100190, China; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
2
Molecular Reaction Dynamics Laboratory, Beijing National Laboratory for Molecular Sciences, Beijing 100190, China; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
3
Institute of Opto-Electronics, Shanxi University, Taiyuan 030006, China.
4
Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
5
Key Laboratory of Energy Conversion and Storage Materials of Shanxi Provence, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China. Electronic address: wanghf@sxu.edu.cn.
6
Molecular Reaction Dynamics Laboratory, Beijing National Laboratory for Molecular Sciences, Beijing 100190, China; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: jwang@iccas.ac.cn.

Abstract

The characteristic nitrosyl stretching (NO) in the region of 1800-1900cm(-1) was used to study the geometric and ligand effect on two nitrosylruthenium complexes, namely [Ru(OAc)(2QN)2NO] (QN=2-chloro-8-quinolinol (H2cqn) or QN=2-methyl-8-quinolinol (H2mqn)). The NO stretching frequency (νNO) was found in the following order: νcis-1 (2cqn)>νcis-2 (2cqn)>νcis-1 (2mqn)>νtrans (2mqn). The results exhibited a spectral sensitivity of the NO mode to both charge distribution and ligand arrangement, which was supported by ab initio computations and natural bond orbital (NBO) analyses. Further, the vibrational population of the vibrationally excited NO stretching mode was found to relax on the order of 7-10ps, showing less than 30% variation from one isomer to another, which were explained on the basis of NO local structures and solute-solvent interactions in these isomeric nitrosylruthenium complexes.

KEYWORDS:

Femtosecond IR pump-probe spectroscopy; Isomer; Nitrosyl; Ruthenium complex; Structural dynamics

PMID:
27209490
DOI:
10.1016/j.saa.2016.04.055

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