While 2a is virtually non-emissive in CH2Cl2 at room temperature, phosphorescence with a lifetime of 1.3 × 10 2 ms was observed in 2-methyltetrahydrofuran (2-MeTHF) at 77 K (Figure ). Transient absorption spectroscopy indicated that intersystem crossing proceeds rapidly with a time constant of 3 ps (Figure ). The CD and CPL spectra of (M,M)-2a and (P,P)-2a are shown in Figure . The CPL g values, |gCPL|, reach 3.3 × 10 -2 at 447 nm, which is higher than those of previously reported organic molecules. Next, we examined transformations of the carbonyl groups of eightphenone 2a (Figure ). Hydrogenation with sodium borohydride (NaBH4) proceeded smoothly at room temperature to afford diol 3 in 89% yield with a syn/anti ratio of 5:3. Treatment with 1.2 equiv of triisopropylethynyllithium furnished the corresponding mono-adduct (4) in 96% yield. A Wittig reaction with in-situ-generated methylenetriphenylphosphorane transformed the carbonyl groups into exo-methylene groups, providing 5 in 4% yield. A single-crystal X-ray diffraction analysis of 5 revealed a distorted ring conformation. The formation of this conformation is likely due to the destabilization of the figure-eight conformation by the steric repulsion between the exo-methylene units and the phenyl groups.