Mixed-Metal-Atom Markers Enable Simultaneous Imaging of Spatial Distribution in Two-Dimensional Heterogeneous Molecular Assembly by Scanning Transmission Electron Microscopy

[Image: see text] Atomic-scale observation by aberration-corrected scanning transmission electron microscopy (STEM) is essential for characterizing supramolecular assemblies with nonperiodic structures. Identifying the relative spatial arrangement in a mixture of molecular species in an assembly is crucial for understanding chemical reaction systems occurring in the assembly. Herein, we report the first direct observation of supramolecular assemblies comprising anionic clay mineral nanosheets and two types of cationic porphyrin complexes with Pt and Pd atom markers by annular dark-field STEM, enabling the simultaneous imaging of well-mixed spatial molecular distributions. The results expand the possibility of applying electron microscopy to self-assembly structures constructed via weak supramolecular interactions on relatively thick nanosheet materials and on one- to few-atom-thick graphene analogues, which will provide important guidelines for future material design.