Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores

Two-dimensional (2D) structures have been shown to possess interesting and potentially useful properties. Because of their isotropic structure, however, clusters tend to assemble into 3D

architectures. Here we report the assembly of polyoxometalate clusters into layered structures that feature uniform hexagonal pores and in-plane electron delocalization properties. Because

these structures are 2D and visually reminiscent of graphene, they are referred to as ‘clusterphenes’. A series of multilayer and monolayer clusterphenes have been constructed with 13 types

of polyoxometalate cluster. The resulting clusterphenes were shown to exhibit substantially improved stability and catalytic efficiency towards olefin epoxidation reactions, with a turnover

frequency of 4.16 h−1, which is 76.5 times that of the unassembled clusters. The catalytic activity of the clusterphenes derives from the electron delocalization between identical clusters

within the 2D layer, which efficiently reduces the activation energy of the catalytic reaction.

All the data supporting the findings of this study are available within the article and its Supplementary Information and also from the corresponding authors upon reasonable request.

This work was supported by the National Key R&D Program of China (2017YFA0700101), NSFC (22035004), the XPLORER PRIZE, the China National Postdoctoral Program for Innovative Talents

(BX2021145) and Shuimu Tsinghua Scholar Program. We thank X. Xu for his help with density functional theory calculations.

Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, China

Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

School of Materials Science and Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, China

X.W. proposed and guided the project. Q.L. designed, planned and carried out the experiments and analysed data. Q.Z. performed the TEM imaging and analysis. W.S. performed the MD

simulations. H.H. performed the density functional theory calculations. J.Z. performed the gas chromatography mass spectrometry tests. All authors discussed the results and commented on the

manuscript.

Nature Chemistry thanks Panchao Yin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Methods, Figs. 1–25, Tables 1–9 and references.

Configurations of assemblies before and after MD simulations.

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