All Single-crystal X-ray diffraction (SCXRD) analysis offered comprehensive structural insights into these three NCs (Table ). The analysis revealed that Cu11PTT crystallizes in a hexagonal crystal system, specifically adopting the space group P63 (No. 173). In contrast, both Cu11ABT and Cu18PTT NCs display distinct crystallographic characteristics, crystallizing in a triclinic crystal system with the space group P-1 (No. 2). Detailed structural analysis of the Cu11PTT NC unveils an intriguing arrangement where a Cu5 triangular bipyramid core is intricately enveloped by three Cu2S3P2 motif units (Figure ). Within the core, the average Cu-Cu distance measures 3.0082±0.0745Å, indicative of a weak coprophilic interaction where the total length of the core is 3.9521Å. In the surrounding motif shell, the Cu-S bond lengths ranging from 2.2431 to 2.3092Å (average 2.2818±0.0133Å), while the Cu-P bond lengths vary between 2.1976 and 2.2268Å (Average 2.2104±0.0044Å). It has been observed that each thiolate ligands coordinate with three Cu atoms, yet there is a discernible discrepancy in their choice of coordinated Cu atoms between core and shell. As, each motif shell contains two terminal thiolate ligands, which are additionally anchored to two Cu atoms from the core. Conversely, the middle thiolate ligand, bridging the two terminal Cu atoms of the motif, interacts with only one Cu atom from the core. This intricate coordination pattern underscores the complexity and precision of the Cu11PTT NC architecture. Although the alteration of PTT ligands by ABT does not change the overall core-shell structural geometry of the NC, but we identified a relatively confined core structural architecture (Figure ). The average Cu-Cu distance measures 2.8384±0.0132Å within the Cu5 core, indicate relatively a stronger coprophilic interaction which ultimately reduces the total length of the core to 3.5494Å than previous. In the surrounding motif shell, the Cu-S bond lengths range from 2.2224 to 2.2936Å (average 2.2566±0.0073Å), while the Cu-P bond lengths vary between 2.2009 and 2.2178Å (Average 2.2093±0.0022Å).