X‑ray Crystal Structure and Optical Properties of Au38–xCux(2,4-(CH3)2C6H3S)24 (x = 0–6) Alloy Nanocluster

In this work, we report the synthesis and crystal structure of Au38–x­Cux­(2,4-DMBT)24 (x = 0–6, 2,4-DMBTH = 2,4-dimethyl­benzene­thiol) alloy nanocluster for the first time. A variety of characterizations including ESI-MS, TGA, and XPS reveal the composition as Au38–x­Cux­(2,4-DMBT)24 (x = 0–6). The single crystal structure has been determined by an X-ray single crystal diffractometer. From the anatomy of the structure, a bi-icosahedral Au23 core is protected by six dimeric [−SR–M–SR–M–SR−] units (M = Cu/Au) and three monomeric [−SR–Au–SR−] units. It is interesting that all the Cu atoms are selectively doped in the motifs of the Au38–x­Cux­(2,4-DMBT)24 nanocluster. This phenomenon is distinct from the exclusive core doping of the Ag atoms in the previously reported Au38–x­Agx alloy. Both the experimental results and DFT calculations of UV–vis spectra imply that the optical property of the Au38–x­Cux­(2,4-DMBT)24 nanocluster is consistent with that of the Au38­(2,4-DMBT)24 nanocluster, because the Cu dopants make little contribution to the frontier orbitals of the alloy NC.