Chiroptical Activity from an Achiral Biological Metal–Organic Framework

Chiroptical activity is observed from an achiral adenine-containing metal-organic framework (MOF) named ZnFDCA. Such a seemingly counterintuitive phenomenon can, in fact, be predicted by the intrinsic crystal symmetry of 4̅2 m point group. Although theoretically allowed, examples of optically active achiral crystals are extremely rare. ZnFDCA is the first reported achiral MOF showing optical activity, as demonstrated by a pair of circular dichroism signals with opposite signs and enhanced intensity. Moreover, simply through adding an amino substituent to adenine, the chiroptical activity, as well as nonlinear optical activity, of the analogous MOF, namely ZnFDCA-NH2, disappears due to diverse packing pattern giving rise to centrosymmetric crystal symmetry.