[Ln6O8] Cluster-Encapsulating Polyplumbites as New Polyoxometalate Members and Record Inorganic Anion-Exchange Materials for ReO4 - Sequestration.

Various types of polyoxometalates (POMs) have been synthesized since the 19th century, but their assortment has been mostly limited to Groups 5 and 6 metals. Herein, a new family of POMs composed of a carbon group element as the addenda atoms with two distinct phases, LnPbOClO4-1 (Ln = Sm to Ho, Y) and LnPbOClO4-2 (Ln = Er and Tm) is reported. Both structures are built from [Ln6O8] rare-earth metal hexamers being incorporated in [Pb18O32]/[Pb12O24] polyplumbites, and unbound perchlorates as charge-balancing anions. Impressively, YPbOClO4-1 and ErPbOClO4-2 exhibit exceptional uptake capacities (434.7 and 427.7 mg g-1) toward ReO4 -, a chemical surrogate for the key radioactive fission product in the nuclear fuel cycle 99TcO4 -, which are the highest values among all inorganic anion-exchange materials reported until now. The sorption mechanism is clearly elucidated and visualized by single-crystal-to-single-crystal structural transformation from ErPbOClO4-2 to a perrhenate-containing complex ErPbOReO4 , revealing a unique ReO4 - uptake selectivity driven by specific interaction within Pb···O-ReO3 - bonds.