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Open Access Publications from the University of California

Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production.

  • Author(s): Tian, Jia
  • Xu, Zi-Yue
  • Zhang, Dan-Wei
  • Wang, Hui
  • Xie, Song-Hai
  • Xu, Da-Wen
  • Ren, Yuan-Hang
  • Wang, Hao
  • Liu, Yi
  • Li, Zhan-Ting
  • et al.
Abstract

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.

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