Cascade polymeric architecture possessing internal functionalities was employed for the preparation of metallo- and nonmetallo-Micellane(TM) derivatives. Specifically, tetra- and dodeca-o-carborane superclusters, were obtained via treatment of the corresponding 1st and 2nd generation tetra- and dodeca-alkyne, hydrocarbon cascade (Micellane(TM)) derivatives with decaborane. Reaction of the same polyalkyne dendritic precursors with Co2(CO)8 afforded the benzyl protected, Cobaltomicellanes(TM) possessing 12 and 24 internal metal centers, respectively. Control of amide-based, carboxylic acid terminated macromolecular hydrodynamic radius via changes in solution pH was demonstrated. Heterocascade syntheses employing amide and metalligand monomer connectivity were accomplished. The relation of interior cascade reactivity to macromolecular 'void volume' was examined.
