A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation

Lanthanide-containing clusters are synthetically Lanthanide-containing clusters are synthetically challenging and with significant chemical and materials applications. Herein, two isostructural heterometallic clusters of the formula (NO3)12@[Ln132Ni78(OH)292(IDA)48(CH3COO)96(NO3)12(H2O)78]Cl44·xH2O·yCH3OH (IDA = iminodiacetate; Ln = Gd 1, x = 110, y = 0; Ln = Eu 2, x = 95, y = 40) were obtained via co-hydrolysis of Ln3+ (Gd3+ or Eu3+) and Ni2+ in the presence of iminodiacetate (IDA). Crystallographic studies show that each features a truncated tetrahedral core of Ln132Ni78 within which a void of 5.5 Å in diameter; connecting the central cage and its exterior are four trumpet-like passageways surface-decorated with dinuclear units of [Gd(μ3-OH)2Gd]. Mass spectroscopic analyses indicate that both clusters maintained their structural integrity in aqueous solution, with cryo-electron microscopy providing the most convincing visual evidence in support of the cluster's solution stability. Size-selective Knoevenagel condensation, believed to occur in the passageways on the basis of experimental and molecular modeling results, was achieved in the presence of 1. The application of 1 as a uniquely structured molecular reactor and a recyclable heterogeneous catalyst was further illustrated by the one-pot three-component synthesis of biologically and pharmaceutically significant 4H-pyran derivatives.