Photochromic Ruthenium Sulfoxide Complexes: Evidence for Isomerization Through a Conical Intersection

摘要: The complexes [Ru(bpy)2(OS)](PF6) and [Ru(bpy)2(OSO)](PF6), where bpy is 2,2′-bipyridine, OS 2-methylthiobenzoate, OSO 2-methylsulfinylbenzoate, have been studied. electrochemical photochemical reactivity of [Ru(bpy)2(OSO)]+ consistent with an isomerization the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or oxidation. Charge transfer excitation in MeOH results appearance two new metal-to-ligand charge (MLCT) maxima at 355 496 nm, while peak 396 nm diminishes intensity. reversible room temperature alcohol propylene carbonate solution. In absence light, solutions O-[Ru(bpy)2(OSO)]+ revert S-[Ru(bpy)2(OSO)]+. Kinetic analysis reveals a biexponential decay rate constants 5.66(3) × 10−4 s−1 3.1(1) 10−5 s−1. Cyclic voltammograms S-[Ru(bpy)2(OSO)]+ are electron-transfer-triggered sulfoxide. Analy...