Piezoelectric Transition in a Nonpyroelectric Gyroidal Metal–Organic Framework

Among the thirty-two crystallographic point groups, 432 is the only one that lacks an inversion center but does not exhibit piezoelectricity. A gyroidal structure belongs to point group 432 and shows characteristic physical properties attributed to its distinctive strong isotropic network. Here, we investigate a gyroidal cobalt oxalate metal-organic framework (MOF) with disordered orientations of SO₄ tetrahedra. Synchrotron X-ray diffraction experiments using a single crystal reveal a cubic-to-cubic structural phase transition at <i>T</i>_S = 120 K. This transition involves a change in the point group from nonpiezoelectric 432 to piezoelectric 23. The symmetry change arises from the ordering of distorted SO₄ molecules, leading to a three-dimensional helical arrangement of electric dipole moments. Furthermore, pyroelectric current measurements using polycrystalline pellet samples reveal that electric polarization emerges below <i>T</i>_S depending on the magnitude of the pelletizing pressure, demonstrating piezoelectricity. The gyroidal MOF offers an opportunity to explore unique dielectric properties induced by the helical ordering of molecules and structural flexibility.