Assembly and Stepwise Oxidation of Interpenetrated Coordination Cages Based on Phenothiazine

The air-sensitive nature of white phosphorus underlies its destructive effect as a munition: Tetrahedral P4 molecules readily react with atmospheric dioxygen, leading this form of the element to spontaneously combust upon exposure to air. Here, we show that hydrophobic P4 molecules are rendered air-stable and water-soluble within the hydrophobic hollows of self-assembled tetrahedral container molecules, which form in water from simple organic subcomponents and iron(II) ions. This stabilization is not achieved through hermetic exclusion of O2 but rather by constriction of individual P4 molecules; the addition of oxygen atoms to P4 would result in the formation of oxidized species too large for their containers. The phosphorus can be released in controlled fashion without disrupting the cage by adding the competing guest benzene.