High pressure has been recognized as an important tool in molecule and materials research, and thus, it is expected to be used to understand the evolution of electronic states and geometric structures in superatoms. In this work, by studying three characteristic axial compressions on a typical endohedral metallofullerene superatom U@C28 with Td symmetry, we find that the triplet ground electronic state is preserved when the compression moves along the direction that reduces the symmetry to D2d, but the electronic state of the structure compressed along the direction of symmetry reduction to C2v or Cs is transformed into a singlet. The transition is attributed to the distinction in the response of electron spin to different axial compressions, which results in a change in the electron occupation mode of the system. Furthermore, we also confirm the gradual evolution from stereo to near-plane superatoms and the connection between their electron structures. This is reflected in the fact that the electron density distributions of the superatomic molecular orbitals (SAMOs) with extension along the restricted degrees of freedom (, SAMOs) gradually contract, and the delocalization destruction of special orbitals is associated with this freedom. In addition, Raman and ultraviolet–visible spectra show a hyperchromic effect and redshift of characteristic peaks during axial compression, which are expected to be used for fingerprinting the superatomic planarization. Therefore, our work provides new insights based on high pressure for future research toward the discovery of physical properties and applications of superatoms.
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