Coordination-Driven Self-Assembly of a 2D Graphite-Like Framework Constructed from High-Nuclear Ce10 Cluster Encapsulated Polyoxotungstates

It is challenging to explore and prepare high-nuclear lanthanide (Ln) cluster-encapsulated polyoxometalates (POMs). Herein, we fabricate an unprecedented Ce10-cluster-embedded polyoxotungstate (POT) (TMA)14H2­[CeIII(H2O)6]­{[CeIV 7CeIII 3O6­(OH)6(CO3)­(H2O)11]­[(P2W16O59)]3}·41H2O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [CeIV 7CeIII 3O6(OH)6­(CO3)­(H2O)11] (Ce10) in all the Ln-containing POM chemistry to date. Self-assembly of the in situ dilacunary [P2W16O59]12– fragments and mixed Ce3+ and Ce4+ ions by means of coordination-driven force results in a novel 2D graphite-like framework constructed from mixed-valent cerium­(III/IV) cluster {Ce10} encapsulated poly­(POT) units and Ce3+ ions. The most remarkable feature is that the skeleton of the centrosymmetric Ce10-cluster-embedded POT trimer contains three dilacunary [P2W16O59]12– fragments trapping a novel {Ce10} cluster via 18 terminal-oxo and three μ4-oxo atoms.