Abstract
Uranium trioxide UO3 reacts with cucurbit[5]uril (CB5) under hydrothermal conditions and in the presence of perrhenic acid to give [UO2(CB5)](ReO4)2·2H2O (1) in which the uranyl ion is encompassed by the five oxygen atoms of one CB5 portal, giving an open molecular capsule. When uranyl nitrate is reacted with CB5 in the presence of alkali metal salts, mixed capsules, capped by one uranyl ion at one portal and K+ or Cs+ at the other, are obtained either as discrete dicationic species in [UO2(CB5)K(NO3)][UO2(NO3)4]·H2O (2) or as part of pentanuclear dicationic assemblages in {[UO2(CB5)Cs(NO3)]2[UO2(NO3)4]}[UO2(NO3)4]·2H2O (3). Finally, the reaction of UO3 with CB5 in the presence of KOH or CsOH, with addition of formic acid, resulted in the formation of the compounds [K2(CB5)(H2O)][(UO2)2(HCOO)(OH)4]2·6H2O (4) and [Cs2(CB5)(H2O)2][(UO2)2(HCOO)(OH)4]2·3H2O (5). In these cases, the uranyl ions are separated from CB5 to form a uranyl/formate/hydroxide two-dimensional assemblage; CB5 capsules capped by K+ or Cs+ at both portals are bound to successive uranyl-organic layers to give a three-dimensional framework of unprecedented architecture.
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