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 Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ and anionic Ag₂₄Au(2‐EBT)₁₈]^? nanoclusters gather and assemble in an unusual alternating array stacking structure is presented. Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ Ag₂₄Au(2‐EBT)₁₈]^? is a new compound type, a double nanocluster ion compound (DNIC). A single nanocluster ion compound (SNIC) PPh₄]⁺ Ag₂₄Au(2‐EBT)₁₈]^? was also synthesized, having a k‐vector‐differential crystallographic arrangement. PPh₄]⁺ Ag₂₄Au(2,4‐DMBT)₁₈]^? adopts a different assembly mode from both Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ Ag₂₄Au(2‐EBT)₁₈]^? and PPh₄]⁺ Ag₂₄Au(2‐EBT)₁₈]^?. Thus, the striking packing differences of Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ Ag₂₄Au(2‐EBT)₁₈]^?, PPh₄]⁺ Ag₂₄Au(2‐EBT)₁₈]^? and the existing PPh₄]⁺ Ag₂₄Au(2,4‐DMBT)₁₈]^? from each other indicate the notable influence of ligands and counterions on the self‐assembly of nanoclusters.