The spontaneous assembly of subnanometer-ordered domains in the ligand shell of monolayer-protected nanoparticles is discussed. The properties of materials can be created and improved either by confining their dimensions in the nanoscale or by controlling their nanostructure. A new class of nanostructured nanosized materials that show ordered phase-separated domains at an unprecedented molecular length scale is described. Scanning tunneling and transmission electron microscope images of monolayer-protected metal nanoparticles, with ligand shells composed of a mixture of molecules, show that the ligands phase-separate into ordered domains.
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