Inorganic Chemistry, Vol.55, No.2, 918-924, 2016
Coordination-Driven Self-Assembly of a 2D Graphite-Like Framework Constructed from High-Nuclear Ce-10 Cluster Encapsulated Polyoxotungstates
It is challenging to explore and prepare high-nuclear lanthanide (Ln) cluster-encapsulated polyoxometalates (POMs). Herein, we fabricate an unprecedented Ce-10-cluster-embedded polyoxotungstate (POT) (TMA)(14)H-2[Ce-III(H2O)(6)]{[(Ce7Ce3O6)-Ce-IV-O-III(OH)(6)(CO3)(H2O)(11)][(P2W16O59)](3)}center dot 41H(2)O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [(Ce7Ce3O6)-Ce-IV-O-III(OH)(6)(CO3)(H2O)(11)] (Ce-10) 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 {Ce-10} 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 {Ce-10} cluster via 18 terminal-oxo and three mu(4)-oxo atoms.