Au24(SAdm)16 Nanomolecules: X-ray Crystal Structure, Theoretical Analysis, Adaptability of Adamantane Ligands to Form Au23(SAdm)16 and Au25(SAdm)16, and Its Relation to Au25(SR)18

Here we present the crystal structure, experimental and theoretical characterization of a Au24(SAdm)16 nanomolecule. The composition was verified by X-ray crystallography and mass spectrometry, and its optical and electronic properties were investigated via experiments and firstprinciples calculations. Most importantly, the focus of this work is to demonstrate how the use of bulky thiolate ligands, such as adamantanethiol, versus the commonly studied phenylethanethiolate ligands leads to a great structural flexibility, where the metal core changes its shape from five-fold to crystalline-like motifs and can adapt to the formation of Au24±1(SAdm)16, namely, Au23(SAdm)16, Au24(SAdm)16, and Au25(SAdm)16. The basis for the construction of a thermodynamic phase diagram of Au nanomolecules in terms of ligands and solvent features is also outlined.