Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells−Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.
We propose a scheme to realize the storage and retrieval of high-dimensional electromagnetic waves with orbital angular momentum (OAM) via plasmon-induced transparency (PIT) in a metamaterial, which consists of an array of meta-atoms constructed by a metallic structure loaded with two varactors. We show that due to PIT effect the system allows the existence of shape-preserving dark-mode plasmonic polaritons, which are mixture of electromagnetic-wave modes and dark oscillatory modes of the meta-atoms and may carry various OAMs. We demonstrate that the slowdown, storage and retrieval of multi-mode electromagnetic waves with OAMs can be achieved through the active manipulation of a control field. Our work raises the possibility for realizing PIT-based spatial multi-mode memory of electromagnetic waves and is promising for practical application of information processing with large capacity by using room-temperature metamaterials.
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