Upon a detailed comparison with the existing literature, a remarkable resemblance is observed between the structural architecture of the Cu11 NCs and the previously reported [Cu11(TBBT)9(PPh3)6] 2+ (Cu11TBBT) NC (TBBT: 4-tert-butylbenzenethiolate) which was synthesized by using NaBH4 as reducing agent. A comparison of the synthetic routes highlights the influence of ligand electronic and steric effects. The PTT ligand, leveraging its hyperconjugation and inductive effects, enhances electron donation to Cu(I) atoms, enabling the formation of the initial complexation and allowing NC synthesis with a mild reducing agent. In contrast, the ABT and TBBT ligands, where the initial complexation is primarily governed by inductive effects, require stronger reducing agents for NC formation. Although, all Cu11 NCs exhibit similar core geometries and motif arrangements, a weaker cuprophilic interaction is evident in the core geometry of Cu11TBBT NC, likely due to differences in the thiolate ligands employed, resulting in a slightly larger core size of 3.9699 Å (Figure ). However, the compressed core structure of the Cu11ABT NC likely results from reduced steric interactions among the outer ligands, promoting a more compact arrangement. Comparing the Cu18PTT NC with the reported [Cu18H3(SAdm)12(PPh3)4Cl2] (Cu18SAdm) NC (SAdm: adamantanethiolate) reveals distinct structural differences due to the variation in thiolate ligands (Figure ). While both NCs share a core-shell architecture formed through a fusion process, the reported NC features the fusion of two distinct geometries, unlike the one discussed here. This highlights the critical role of thiolate ligands, reducing agents, and reaction conditions in precisely controlling NC geometries.