One photon yields two isomerizations: large atomic displacements during electronic excited-state dynamics in ruthenium sulfoxide complexes

J Am Chem Soc. 2014 Feb 5;136(5):1856-63. doi: 10.1021/ja409262r. Epub 2014 Jan 27.

Abstract

Photochromic compounds efficiently transduce photonic energy to potential energy for excited-state bond-breaking and bond-forming reactions. A critical feature of this reaction is the nature of the electronic excited-state potential energy surface and how this surface facilitates large nuclear displacements and rearrangements. We have prepared two photochromic ruthenium sulfoxide complexes that feature two isomerization reactions following absorption of a single photon. We show by femtosecond transient absorption spectroscopy that this reaction is complete within a few hundred picoseconds and suggest that isomerization occurs along a conical intersection seam formed by the ground-state and excited-state potential energy surfaces.