Electron Crystallography Reveals Atomic Structures of Metal–Organic Nanoplates with M₁₂(μ₃‑O)₈(μ₃‑OH)₈(μ₂‑OH)₆ (M = Zr, Hf) Secondary Building Units

Nanoscale metal–organic frameworks (nMOFs) have shown tremendous potential in cancer therapy and biomedical imaging. However, their small dimensions present a significant challenge in structure determination by single-crystal X-ray crystallography. We report here the structural determination of nMOFs by rotation electron diffraction (RED). Two isostructural Zr- and Hf-based nMOFs with linear biphenyldicarboxylate (BPDC) or bipyridinedicarboxylate (BPYDC) linkers are stable under intense electron beams to allow the collection of high-quality RED data, which reveal a MOF structure with M₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆ (M = Zr, Hf) secondary building units (SBUs). The nMOF structures differ significantly from their UiO bulk counterparts with M₆(μ₃-O)₄(μ₃-OH)₄ SBUs and provide the foundation for clarifying the structures of a series of previously reported nMOFs with significant potential in cancer therapy and biological imaging. Our work clearly demonstrates the power of RED in determining nMOF structures and elucidating the formation mechanism of distinct nMOF morphologies.