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摘要
A dispersion-corrected DFT study on the redox-induced linkage isomerization of a family of [M(bpy)2AL](2+) complexes {M = Ru, Os; bpy = 2,2-bipyridine; AL = 2-[(isopropylsulfinyl)methyl]pyridine (pySO), 2-[2-(isopropylsulfinyl)ethyl]pyridine (pyESO), 2-[3-(isopropylsulfinyl)propyl]pyridine (pyPSO)} was undertaken. The calculated results indicated that modification of the metal center or ancillary ligand could produce distinct electronic and photophysical properties of the complexes. In good agreement with experimental absorption spectrum results, a redshift in the absorption maximum was observed if the metal center of the complex was changed from ruthenium to osmium. More importantly, the relative thermodynamic stabilities of the two linkage isomers in these complexes could also be tuned by modifications to the metal center or ancillary ligand. It was found that the relative energies between the S- and O-linked ruthenium sulfoxide complexes were smaller than those between the osmium sulfoxide isomers. Intrinsic reaction pathway results demonstrated that intramolecular SO and OS isomerization was easier in the ruthenium complexes than in the osmium complexes with the same coordinated ligands. Moreover, intramolecular isomerization was more favorable if the number of methylene units between the sulfoxide group and the pyridine ring in the ancillary ligand was increased.
- 出版日期2015-10
- 单位赣南师范大学
