The elaborate selection of capping ligands is of great importance in the synthesis of atomically precise metal nanoclusters. Organic thiolates, alkynyls, phosphines, and/or their combinations are the ligands most widely utilized to protect metal nanoclusters, while inorganic oxo anions have been almost neglected in this field. Herein, the first CrO 4 2− / t BuCC − co-capped Ag 48 nanocluster (SD/Ag48, SD = SunDi) was synthesized and structurally characterized by single-crystal X-ray diffraction. The pseudo-5-fold symmetric metal skeleton of SD/Ag48 shows a core−shell structure composed of a Ag 23 cylinder encircled by an outer Ag 25 shell. Unprecedentedly, coexistence of inorganic (CrO 4 2− ) and organic ( t BuCC − ) ligands was observed on the surface of SD/Ag48. The inorganic CrO 4 2− anion plays three important roles in the construction of silver nanoclusters: (i) passivating the Ag 23 kernel; (ii) connecting the core and shell; and (iii) protecting the Ag 25 shell. This nanocluster belongs to a 14e superatom system and exhibits successive molecule-like absorption bands from the visible to the ultraviolet region. This work not only establishes a fresh inorganic ligand strategy in the synthesis of silver nanoclusters but also provides a new insight into the important surface coordination chemistry of CrO 4 2− in the shape control of silver nanoclusters.

Cluster models are used in calculation of (207)Pb NMR magnetic-shielding parameters of α-PbO, β-PbO, Pb3O4, Pb2SnO4, PbF2, PbCl2, PbBr2, PbClOH, PbBrOH, PbIOH, PbSiO3, and Pb3(PO4)2. We examine the effects of cluster size, method of termination of the cluster, charge on the cluster, introduction of exact exchange, and relativistic effects on calculation of magnetic-shielding tensors with density functional theory. Proper termination of the cluster for a network solid, including approximations such as compensation of charge by the bond-valence (BV) method, is essential to provide results that agree with experiment. The inclusion of relativistic effects at the spin-orbit level for such heavy nuclei is an essential factor in achieving agreement with experiment.

We investigate the doping process theoretically for singly doped MAu24, MAg24, and MAu37 (M = Ni, Pd, Pt, Cu, Ag/Au, Zn, Cd, Hg, Ga, In, and Tl) clusters using density functional theory (DFT). For all clusters, the group X dopants (Ni, Pd, and Pt) prefer the central location due to the relative stability of d electrons in the dopant. For dopants in groups XI–XIII, doping on the surface of the core and the ligand shell in MAu24 becomes thermodynamically more preferable as a result of symmetry-dictated coupling between dopant atomic orbitals and superatomic levels as well as because of relativistic contraction of s and p orbitals. The same mechanisms are also found to be responsible for the relative isomer energies in MAu37 clusters. For these clusters, DFT calculations predict that it is unlikely for the dopant atom to occupy the central location. We found similar trends for different dopants across the periodic table in relative isomer energies of MAu24 and MAg24; however, center-doped clusters are somewhat more stable in the case of MAg24 due to the smaller relativistic stabilization of s and p levels in Ag compared to Au. We also found that the metallic radii of the dopant can affect the geometries and relative stabilities of the isomers for the doped clusters significantly.