title: Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production.
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.
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Jia
authors.initials: J
authors.lastname: Tian
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Zi-Yue
authors.initials: ZY
authors.lastname: Xu
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Dan-Wei
authors.initials: DW
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Hui
authors.initials: H
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Song-Hai
authors.initials: SH
authors.lastname: Xie
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Da-Wen
authors.initials: DW
authors.lastname: Xu
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Yuan-Hang
authors.initials: YH
authors.lastname: Ren
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Hao
authors.initials: H
authors.lastname: Wang
authors.affiliation: The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Yi
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fudan University, Shanghai 200433, China.
authors.forename: Zhan-Ting
authors.initials: ZT
authors.lastname: Li