title: Photoisomerization and structural dynamics of two nitrosylruthenium complexes: a joint study by NMR and nonlinear IR spectroscopies.
abstract: In this work, the photoisomerization and structural dynamics of two isomeric nitrosylruthenium(ii) complexes [Ru(OAc)(2cqn)2NO] (H2cqn = 2-chloro-8-quinolinol) in CDCl3 and DMSO are examined using NMR and IR spectroscopic methods. The two N atoms in the 2cqn ligand are in trans position in the synthesized cis-1 isomer, while they are in cis position in the cis-2 isomer. Kinetics monitored by NMR spectroscopy shows that the rate constant of photoisomerization from cis-2 to cis-1 isomer depends on the wavelength of irradiation and solvent polarity; it proceeds faster on irradiating near the absorption peak in the UV-Vis region, and also in more polar solvents (DMSO). Density functional theory computation indicates that the peculiarity of [Ru(ii)-NO(+)] group affects the structure and reactivity of the nitrosylruthenium complexes. Using the nitrosyl stretching (νNO) to be vibrational probe, the structural dynamics and structural distributions of the cis-1 and cis-2 isomers are examined by steady-state linear infrared and ultrafast two-dimensional infrared (2D IR) spectroscopies. The structural and photochemical aspects of the observed spectroscopic parameters are discussed in terms of solute-solvent interactions for the two nitrosylruthenium complexes.
authors.affiliation: State Key Lab of Quantum Optics and Quantum Optics Devices, Institute of Opto-Electronics, Shanxi University, Taiyuan 030006, China. wanghf@sxu.edu.cn.
authors.forename: Jianru
authors.initials: J
authors.lastname: Wang
authors.forename: Fan
authors.initials: F
authors.lastname: Yang
authors.forename: Yan
authors.initials: Y
authors.lastname: Zhao
authors.forename: Pengyun
authors.initials: P
authors.lastname: Yu
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Qiao
authors.forename: Jianping
authors.initials: J
authors.lastname: Wang
authors.forename: Hongfei
authors.initials: H
authors.lastname: Wang