Alternating Array Stacking of Ag₂₆Au and Ag₂₄Au Nanoclusters

An assembly strategy for metal nanoclusters using electrostatic interactions with weak interactions, such as C−H⋅⋅⋅π and π⋅⋅⋅π interactions in which cationic [Ag 26 Au(2‐EBT) 18 (PPh 3 ) 6 ] + and anionic [Ag 24 Au(2‐EBT) 18 ] − nanoclusters gather and assemble in an unusual alternating array stacking structure is presented. [Ag 26 Au(2‐EBT) 18 (PPh 3 ) 6 ] + [Ag 24 Au(2‐EBT) 18 ] − is a new compound type, a double nanocluster ion compound (DNIC). A single nanocluster ion compound (SNIC) [PPh 4 ] + [Ag 24 Au(2‐EBT) 18 ] − was also synthesized, having a k‐vector‐differential crystallographic arrangement. [PPh 4 ] + [Ag 24 Au(2,4‐DMBT) 18 ] − adopts a different assembly mode from both [Ag 26 Au(2‐EBT) 18 (PPh 3 ) 6 ] + [Ag 24 Au(2‐EBT) 18 ] − and [PPh 4 ] + [Ag 24 Au(2‐EBT) 18 ] − . Thus, the striking packing differences of [Ag 26 Au(2‐EBT) 18 (PPh 3 ) 6 ] + [Ag 24 Au(2‐EBT) 18 ] − , [PPh 4 ] + [Ag 24 Au(2‐EBT) 18 ] − and the existing [PPh 4 ] + [Ag 24 Au(2,4‐DMBT) 18 ] − from each other indicate the notable influence of ligands and counterions on the self‐assembly of nanoclusters.