Abstract
Electronic and photophysical properties of [Ru(bpy)2(OSO)]+ (bpy=2,2′-bipyridine; OSO=methylsulfinylbenzoate) were examined theoretically to better understand the differences between S- and O-linked ruthenium sulfoxide complexes. It is found that the strength of Ru–O1 linkage is significantly larger than that of Ru–S linkage, which makes the charge transfer amount from surrounding ligands to central Ru decreased. The energy gap is closed due to the highest occupied molecular orbital energy increases to a larger extent than the lowest unoccupied molecular orbital energy. Thereby, red shifted absorption and emission maxima in such photochromic ruthenium sulfoxide complexes can be explained.
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