Abstract
A structure evolution map of face-centered cubic (fcc)-structured thiolate-ligand protected gold nanoclusters is outlined on the basis of total structure determination of a new 6e Au21(SR)15 (R = tert-butyl, t-Bu) cluster. The structural evolution map described some basic structural evolution patterns such as a triangle-Au3 and tetrahedron-Au4 associated gold-core evolution pattern and the periodic or symmetric growth of gold cores and ligand shells. According to the structural evolution map, a topological structure–electronic structure relationship is also proposed. The delocalized valence electronic properties of any fcc-structured gold clusters may be expressed as the linear combinations of the molecular orbitals of the fragment 2e units (Au3+ and Au42+). The structural disciplines and topological structure–electronic structure relationships reported in this work laid a basis for understanding the structural evolution and electronic structure of fcc-structured thiolate-protected gold nanoclusters. Part...
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