Photoreactivity of crystals of a rhodium dithionite complex with ethyltetramethylcyclopentadienyl ligands: crystal surface morphology changes and degradation.

A photoreactive rhodium dithionite complex [(RhCp(Et))(2)(μ-CH(2))(2)(μ-O(2)SSO(2))] (1(Et)) with Cp(Et) (η(5)-C(5)Me(4)Et) ligands was newly synthesized. Upon short-time irradiation with low intensity light, two kinds of stepwise surface morphology changes of the crystal 1(Et) were observed. Prolonged irradiation with high intensity light caused cracking and breaking down of the crystal.

The absolute asymmetric photoisomerization of a photochromic dithionite complex in chiral crystals.

An achiral photochromic dithionite (micro-O(2)SSO(2)) complex with n-propyl moieties forms chiral crystals and undergoes an enantioselective photoisomerization (ee > 90%) to an oxysulfur (micro-O(2)SOS*O) complex, containing an asymmetric S atom, with essentially 100% interconversion of the chiral crystals.

Photochromism of an organorhodium dithionite complex in the crystalline-state: molecular motion of pentamethylcyclopentadienyl ligands coupled to atom rearrangement in a dithionite ligand.

In the crystalline state, the rhodium dinuclear complex [(RhCp*)(2)(mu-CH(2))(2)(mu-O(2)SSO(2))] (1) with a photoresponsive dithionite group (mu-O(2)SSO(2)) and two pentamethylcyclopentadienyl ligands (Cp* = eta(5)-C(5)Me(5)) undergoes a 100% reversible unimolecular type T inverse photochromism upon interconversion to [(RhCp*)(2)(mu-CH(2))(2)(mu-O(2)SOSO)] (2). The photochromism can be followed directly by using stepwise crystal structure analysis (Angew. Chem.