ABSTRACT 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

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Article 25 June 2024 SYNTHESIS OF TWO-DIMENSIONAL POLYOXONIOBATE-BASED CLUSTERPHENES WITH IN-PLANE ELECTRON DELOCALIZATION Article 18 May 2023 A ZERO-VALENT PALLADIUM CLUSTER-ORGANIC

FRAMEWORK Article Open access 08 February 2024 DATA AVAILABILITY All the data supporting the findings of this study are available within the article and its Supplementary Information and

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Chem. Soc._ 117, 681–691 (1995). Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS 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. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University,

Beijing, China Qingda Liu, Hanshi Hu, Jing Zhuang & Xun Wang * Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

Qinghua Zhang * School of Materials Science and Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, China Wenxiong Shi Authors *

Qingda Liu View author publications You can also search for this author inPubMed Google Scholar * Qinghua Zhang View author publications You can also search for this author inPubMed Google

Scholar * Wenxiong Shi View author publications You can also search for this author inPubMed Google Scholar * Hanshi Hu View author publications You can also search for this author inPubMed 

Google Scholar * Jing Zhuang View author publications You can also search for this author inPubMed Google Scholar * Xun Wang View author publications You can also search for this author

inPubMed Google Scholar CONTRIBUTIONS 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. CORRESPONDING AUTHOR Correspondence to Xun Wang. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. PEER REVIEW

PEER REVIEW INFORMATION _Nature Chemistry_ thanks Panchao Yin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. ADDITIONAL INFORMATION PUBLISHER’S

NOTE Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary

Methods, Figs. 1–25, Tables 1–9 and references. SUPPLEMENTARY DATA 1 Configurations of assemblies before and after MD simulations. SUPPLEMENTARY DATA 2 Atomic coordinates of POM cluster

calculated by DFT. SUPPLEMENTARY DATA 3 Source data for Supplementary Figs. 15 and 16. RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Liu, Q., Zhang,

Q., Shi, W. _et al._ Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores. _Nat. Chem._ 14, 433–440 (2022).

https://doi.org/10.1038/s41557-022-00889-1 Download citation * Received: 24 January 2021 * Accepted: 04 January 2022 * Published: 10 February 2022 * Issue Date: April 2022 * DOI:

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