Isomeric Au 7 Cu 8 Nanoclusters With Identical Building Blocks but Distinct Assembly Modes

ABSTRACT Isomeric metal nanoclusters composed of identical building blocks provide an ideal platform for probing structure–property relationships at the atomic level; however, their controlled synthesis remains highly challenging. Herein, we report the synthesis and structural characterization of two structurally isomeric AuCu nanoclusters, [Au 7 Cu 8 (L) 2 (TBA) 4 Cl 6 ]PF 6 (L = PNP or PMNP, where PNP is 2,6‐bis(diphenylphosphino)pyridine, PMNP is 2,6‐bis(diphenylphosphinomethyl)pyridine, and TBA is tert ‐butylacetylide), denoted as Au 7 Cu 8 ‐ 1 and Au 7 Cu 8 ‐ 2 , respectively. Single‐crystal X‐ray diffraction analysis reveals that both isomers feature an Au 7 Cu 6 core constructed from two pentagonal bipyramidal Au 4 Cu 3 building blocks fused through a common Au atom. The two isomers differ in the assembly mode of the Au 4 Cu 3 units: in Au 7 Cu 8 ‐ 1 , fusion occurs through a gold…