Ligand Engineering toward the Trade‐Off between Stability and Activity in Cluster Catalysis

We report the structures, stability and catalysis properties of two Ag₂₁ nanoclusters, namely [Ag₂₁ (H₂ BTCA)₃ (O₂ PPh₂ )₆ ]SbF₆ (1) and [Ag₂₁ (C≡CC₆ H₃ -3,5-R₂ )₆ (O₂ PPh₂ )₁₀ ]SbF₆ (2) (H₄ BTCA=p-tert-butylthiacalix[4]arene, R=OMe). Both Ag₂₁ structures possess an identical icosahedral kernel that is surrounded by eight peripheral Ag atoms. Single-crystal structural analysis and ESI-MS revealed that 1 is an 8-electron cluster and 2 has four free electrons. Theoretical results show that the P-symmetry orbitals are found as HOMO-1 and HOMO states in 1, and the frontier unoccupied molecular orbitals (LUMO, LUMO+1 and LUMO+2) show D-character, indicating 1 is a superatomic cluster with an electronically closed shell 1S² 1P⁶ , while 2 has an incomplete shell configuration 1S² 1P² . These two Ag₂₁ clusters show superior stability under ambient conditions, and 1 is robust even at 90 °C in toluene and under oxidative conditions (30 % H₂ O₂ ). Significantly, 2 exhibits much higher activity than 1 as catalyst in the reduction of 4-nitrophenol. This work demonstrates that ligands can influence the electronic structures of silver clusters, and further affect their stability and catalytic performance.