An octanuclear cubic coordination cage host has been investigated for (i) its ability to catalyse reactions of bound substrates; and (ii) to effect photoinduced energy- or electron-transfer from the array of chromophores in the cage superstructure to bound guests. Chemical catalysis is based on the ability of the cationic (16+) cage to accumulate anions around its surface which brings them into close proximity to hydrophobic guests which bind in the central cavity in water. Several different substrates undergo reactions promoted by hydroxide ions including an E2 elimination reaction (Kemp elimination), phosphotriester hydrolysis, nucleophilic attack on dinitrofluorobenzene, and an aldol condensation of indane-dione. Whilst some of the catalysed reactions are associated with strong binding of the substrate in the cage cavity, in other cases blocking the cavity with an inert inhibitor makes no difference to catalysis which we believe to be associated with the exterior surface of the cage.<br/><br/>In addition isostructural examples of this cage type can be prepared containing photophysically-active units in the cage: these are either phosphorescent Os(II) complex units at the cage vertices, or fluorescent naphthyl units incorporated into the ligands. Bound guests are therefore surrounded by a large number of chromophores in close proximity, and in several cases we have observed fast photoinduced electron transfer to the guests generating short-lived charge-separated states (host radical cation, guest radical anion) as a precursor to possible photo-redox catalysis in the cage cavity.

Chemical catalytic properties and photophysical properties of a coordination cage host

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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