Discrete, Cationic Palladium(II)‐Oxo Clusters via f‐Metal Ion Incorporation and their Macrocyclic Host‐Guest Interactions with Sulfonatocalixarenes

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We report on the discovery of the first two examples of cationic palladium(II)‐oxo clusters (POCs) containing f ‐metal ions, [Pd II 6 O 12 M 8 {(CH 3 ) 2 AsO 2 } 16 (H 2 O) 8 ] 4+ (M=Ce IV , Th IV ), and their physicochemical characterization in the solid state, in solution and in the gas phase. The molecular structure of the two novel POCs comprises an octahedral {Pd 6 O 12 } 12− core that is capped by eight M IV ions, resulting in a cationic, cubic assembly {Pd 6 O 12 M IV 8 } 20+ , which is coordinated by a total of 16 terminal dimethylarsinate and eight water ligands, resulting in the mixed Pd II ‐Ce IV /Th IV oxo‐clusters [Pd II 6 O 12 M 8 {(CH 3 ) 2 AsO 2 } 16 (H 2 O) 8 ] 4+ (M=Ce, Pd 6 Ce 8 ; Th, Pd 6 Th 8 ). We have also studied the formation of host‐guest inclusion complexes of Pd 6 Ce 8 and Pd 6 Th 8 with anionic 4‐sulfocalix[ n ]arenes ( n =4, 6, 8), resulting in the first examples of discrete, enthalpically‐driven supramolecular assemblies between large metal‐oxo clusters and calixarene‐based macrocycles. The POCs were also found to be useful as pre‐catalysts for electrocatalytic CO 2 ‐reduction and HCOOH‐oxidation.