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A water-soluble metallo-supramolecular polymer MSP-f-6Np, which possesses a regular pore aperture of 1.4 nm, has been assembled from a structurally flexible naphthalene-appended [Ru(bipy)3]2+ complex and cucurbit[8]uril. As the first periodic metallo-supramolecular polymer formed by a flexible building block, MSP-f-6Np exhibits a hydrodynamic diameter of 122 and 164 nm at 0.1 and 2.0 mM of the monomer concentrations. Synchrotron small angle X-ray scattering experiments confirm that MSP-f-6Np possesses porosity periodicity in both the solution and solid states. Compared with a control, the new highly ordered porous system displays enhanced photocatalytic activity for the degradation of organic dyes.

A supramolecular organic framework-type photocatalyst, named TM-SOF, is constructed by the self-assembly of cucurbit [8]uril and a tetra-arm monomer containing four N, N'-dimethyl 2,5-bis(4-pyridinium)thiazolo [5,4-d]thiazole (MPT) moieties. Benefiting from the multivalent assembly, a photocatalytically active supramolecular MPT dimer can be stably formed in TM-SOF. In addition, TM-SOF exhibits better stability against temperature, substrate, and light irradiation. As a result, TM-SOF shows a significantly improved performance for the photocatalytic aerobic oxidation of aryl boronic acids and thioethers. It is anticipated that this line of research will provide a facile approach for fabricating high-performance supramolecular photocatalysis systems.

Solar‐to‐hydrogen conversion is a sustainable way of producing renewable fuels, yet the efficiency is limited by the poor photo‐induced charge‐carrier separation on electrode surface. Developing active and stable hydrogen evolution photocatalysts is challenging and entails intelligent material structure design and tailoring. Here, a novel water dispersible supramolecular metal organic framework (SMOF) is employed as a general and high‐performance platform to encapsulate CdS quantum dots (QDs) for achieving highly improved solar‐induced H2‐production activity. Particularly, the CdS QDs@SMOF heterostructure exhibits an excellent H2 generation activity of 49.4 µmol h−1 (TOF = 47.0/h), exceeding those of most reported heterogeneous metal organic frameworks‐based photocatalytic systems. Advanced characterizations disclose that the strong electrostatic interaction and light‐induced charge transfer between SMOF and CdS QDs, combined with the high surface area, water dispersible nature, and abundant reactive centers synergistically contribute to this distinguished photocatalytic performance. The work not only demonstrates the water dispersible SMOF can serve as a versatile and effective platform supporting semiconductor to boost the photocatalytic H2‐production performance without co‐catalysts, but also paves avenues to the design and synthesis of SMOF‐based heterostructures for general catalysis applications.

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