King Albert W, McClure Beth Anne, Jin Yuhuan, Rack Jeffrey J
Nanoscale and Quantum Phenomena Institute, Department of Chemistry and Biochemistry, Ohio University , Athens, Ohio 45701, United States.
J Phys Chem A. 2014 Nov 13;118(45):10425-32. doi: 10.1021/jp504078g. Epub 2014 Aug 19.
The photochromic complex Ru(bpy)2(pySO) [pySO is 2-(isopropylsulfinylmethyl)pyridine] undergoes wavelength specific, photoreversible S → O and O → S linkage isomerizations. Irradiation of the ground state S-bonded complex with blue light produces the O-bonded isomer, while irradiation of the O-bonded isomer with green light produces the S-bonded isomer. Furthermore, isomerization time constants are solvent-dependent. Ultrafast transient absorption spectroscopy has been employed to investigate the relaxation processes that lead to S → O isomerization in 1,2-dichloroethane, propylene carbonate, and ethylene glycol. The isomerization is most rapid in 1,2-dichloroethane and slowest in ethylene glycol. Photochemical reversion of the O-bonded isomer in propylene carbonate has further been investigated and indicates similar relaxation or isomerization kinetics, though the excited states that lead to isomerization are distinct between the S- and O-bonded isomers.
光致变色配合物Ru(bpy)2(pySO) [pySO为2-(异丙基亚磺酰甲基)吡啶]会发生波长特异性的、光可逆的S→O和O→S键异构化。用蓝光照射基态S键合配合物会产生O键合异构体，而用绿光照射O键合异构体会产生S键合异构体。此外，异构化时间常数取决于溶剂。超快瞬态吸收光谱已被用于研究在1,2-二氯乙烷、碳酸丙烯酯和乙二醇中导致S→O异构化的弛豫过程。异构化在1,2-二氯乙烷中最快，在乙二醇中最慢。对碳酸丙烯酯中O键合异构体的光化学逆转进行了进一步研究，结果表明其弛豫或异构化动力学相似，尽管导致异构化的激发态在S键合异构体和O键合异构体之间有所不同。
