The overall metallic architecture is protected by four hydride atoms, eighteen thiolate ligands, and six triphenylphosphine ligands. The hydride atoms are integrated within the metallic framework, attaching specifically to the regular facets of the cubic structures (Figure ). These hydrides play a critical role in stabilizing the metallic core by reinforcing the interactions between the Cu atoms, thereby maintaining the integrity of the ordered configuration. The eighteen thiolate ligands are strategically positioned around the metallic architecture, providing additional stabilization and preventing aggregation by forming a protective layer around the metal atoms. The Cu-S bond lengths range from 2.2183 to 2.4402 Å, with an average of 2.3157 ± 0.0168 Å. The thiolate ligands exhibit specific coordination modes, categorized into four sub-categories (Figure and Figure ). Four thiolate ligands stabilize the fused structural architecture by exhibiting a μ3 bridging mode, each bridging two Cu atoms from the two elongated square pyramids and another Cu atom from the Cu3 unit. This attachment restricts the structure to a core-shell configuration, forming a Cu₉ geometry that favors a body-centered cubic architecture. Meanwhile, the other eight thiolate ligands protect the four open faces of each cube within the elongated square pyramid geometry, exhibiting a μ4 bridging mode and the Cu23 NC, confirming the successful replacement of hydrides with deuteride atoms.