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Stereospecific solid-state chemical reactions of chiral crystals formed from achiral molecules are defined as absolute asymmetric reactions. We have recently found that a new class of transitionmetal based photochromic compounds, a rhodium dithionite complex [(RhCp*)2(μ-CH2)(μ-O2SSO2)] (1) with a photo-responsive dithionite group (O2SSO2) and two pentamethylcyclopentadienyl ligands (Cp* = η-C5Me5), shows the reversible crystalline-state photochromic reaction with essentially 100% inter conversion ratio. The photochemical atom rearrangement reaction of the dithionite unit can possibly generate enantiomers with R and S absolute configurations originating from an asymmetric sulfur atom in the photoisomerization product. Herein, we present an absolute asymmetric photoisomerization of a new achiral photochromic d i t h i o n i t e complex hav ing n-propyl moieties [(RhCp)2(μ-CH2) (μ-O2SSO2)] (Cp = η5 C 5 M e 4 n Propyl ) (1 ) in chiral crystals.

Photochromism of fulgides: crystalline-state reactions induced by one- and two-photon excitation