ジチオナイト基をもつロジウム二核錯体の結晶相フォトクロミズムとそのダイナミクス
2008 年 50 巻 6 号 p. 348-353
詳細
2008 年 50 巻 6 号 p. 348-353
The compounds that undergo photochromic reaction in the crystalline-state are rare and their reaction dynamics are not well characterized as a result of the low degree of interconversion ratios and/or instability of the photo-generated isomers in the solid phase. We have recently found that a rhodium Binuclear complex [ (RhCp*) 2 (μ-CH2) 2 (μ-O2SSO2) ] (Cp*=η5-C5Me5) having a photo-responsive dithionite group (μ-O2SSO2), undergoes an essentially 100% reversible crystalline-state photochromism upon interconversion to [ (RhCp*) 2 (μ-CH2) 2 (μ-O2SOSO) ] . Taking an advantage of this unique full reversibility, we have investigated the dynamics of the system by using stepwise single crystal diffraction and variable-temperature solid-state NMR technique. The stereospecifc oxygen-atom rearrangement process of the dithionite ligand and reorientational motion of the Cp* ligands, which are coupled to the photochromism, are presented.
