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Exploration of metal clusters (MCs) adaptive to both aqueous and oil phases without disturbing their size is promising for a broad scope of applications. The state-of-the-art approach via ligand-binding may perturb MCs' size due to varied metal–ligand binding strength when shuttling between solvents of different polarity. Herein, we applied physical confinement of a series of small noble MCs (<1 nm) inside ionic organic cages (I-Cages), which by means of anion exchange enables reversible transfer of MCs between aqueous and hydrophobic solutions without varying their ultrasmall size. Moreover, the MCs@I-Cage hybrid serves as a recyclable, reaction-switchable catalyst featuring high activity in liquid-phase NH3BH3 (AB) hydrolysis reaction with a turnover frequency (TOF) of 115 min−1.
Self-assembly of block copolymers is a significant area of polymer science. The self-assembly of completely water-soluble block copolymers is of particular interest, albeit a challenging task. In the present work the self-assembly of a linear-brush architecture block copolymer, namely poly(N-vinylpyrrolidone)-b-poly(oligoethylene glycol methacrylate) (PVP-b-POEGMA), in water is studied. Moreover, the assembled structures are crosslinked via alpha-CD host/guest complexation in a supramolecular way. The crosslinking shifts the equilibrium toward aggregate formation without switching off the dynamic equilibrium of double hydrophilic block copolymer (DHBC). As a consequence, the self-assembly efficiency is improved without extinguishing the unique DHBC self-assembly behavior. In addition, decrosslinking could be induced without a change in concentration by adding a competing complexation agent for alpha-CD. The self-assembly behavior was followed by DLS measurement, while the presence of the particles could be observed via cryo-TEM before and after crosslinking.