A notable redistribution in the arrangement of Cu(I) atoms is observed when the solvent medium in the reaction is altered. In this case, the synthesis of the Cu10-dpb CAM proceeds via the dissolution of the linker molecules in a polar protic solvent, MeOH, as opposed to the previous use of a polar aprotic solvent (DMAc). This change creates an interface between the polar protic and aprotic solutions, initiating the redistribution of the Cu(I) atoms at the reaction environment. As a result, the reaction yields a structure consisting of ten Cu(I) atoms stabilized by six S t Bu -ligands (Fig. ). The rearrangement of Cu atoms also alters the number of attached CF3COO -ligands and dpb linker molecules than the previous (Fig. ). This observation underscores the crucial impact of the solvent environment on the distribution and stabilization of metal atoms during the synthesis process and its effect on the overall cluster node structure. The detailed structural architecture reveals that the larger interatomic distances (3.2829 ± 0.162 Å) limit the ability of the Cu(I) atoms to adopt a specific geometric arrangement. Despite this, strong cuprophilic interactions are observed, particularly in the middle Cu4 layer, where the Cu-Cu distance is measured at 2.6867 Å. This additional Cu4 layer is sandwiched between two Cu3 layers which are previously obtained in the Cu6-dpb, creating a notable structural feature. Among the six thiolate ligands, four engage in a µ4 bridging mode, connecting Cu(I) atoms between the middle and one of the Cu3 layer. The remaining two thiolates utilize a µ3 bridging mode, connecting Cu(I) atoms across the middle and one of the Cu3 layer. The average Cu-S bond distance is 2.2845 ± 0.0408 Å. The four CF3COO -ligands are divided into two groups: two of them bridge the Cu(I) atoms via a µ2 bridging mode, while the other two adopt a µ1 bridging mode. The attachment of four dpb linkers results in the formation of a 2D framework structure, where the linkers are connected diagonally to the two Cu3 layers, similar to the previous arrangement (Fig. ). Notably, the use of a polar protic solvent enables the incorporation of an