On the structure of the thiolated Au₁₅ cluster

The structure of the Au₁₅-thiolate cluster has been elucidated using a DFT approach, and it is demonstrated to comprise a Au ₄-tetrahedron core protected solely by the combination of two concatenated staple motifs. The longer motif efficiently wraps the core, and threads the shorter one. The structural assignment is supported by comparison to the powder X-ray diffraction pattern and, via time dependent-DFT calculations, to the optical and chiroptical (CD) absorption spectra. The calculated CD spectrum features a characteristic strong peak centered at 3.48 eV in accordance with the experimental profile. These results confirm the existence of long Au(i)-thiolate motifs as protecting units of small thiolated gold clusters with a thiolate-to-gold ratio comparable to the Au₁₅(SR)₁₃ cluster.