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Helical polymer metal–organic framework hybrids

Nature Synthesis volume 5, pages 46–54 (2026)Cite this article

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Abstract

Templated polymerization within confined spaces offers a powerful route to tailor polymer structures and properties, yet structural details of confined polymers at the atomic level remain obscure owing to challenges in obtaining high-quality single crystals. Here we report the single-crystal X-ray structures of helical polythiophene and polypyrrole, produced by in situ radical polymerization of achiral monomers in a chiral metal–organic framework (MOF) featuring redox-active tri-iron(III) clusters. Crystallographic analysis reveals that both polymers adopt single-handed helical conformations, stabilized by supramolecular interactions with pore surfaces. Unexpectedly, the helical chains grow through narrow catalytic channels rather than in wide pores, as previously assumed. The confined helicity substantially amplifies the chirality-induced spin selectivity of the MOF, yielding spin polarization of up to 94% and demonstrating the key role of helicity in spin selectivity. Our work lays the foundation for the rational design of single-crystalline porous hybrids with tunable electronic, optical and quantum properties that surpass conventional crystals.

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Fig. 1: Schematic illustration of the mechanism for the synthesis of single-crystal Fe-Spiro@polymers.
Fig. 2: SCXRD structures of (S)-Fe-Spiro@PTh.
Fig. 3: SCXRD structures of (R)-Fe-Spiro@PPy.
Fig. 4: Structural characterization and conductive properties.
Fig. 5: CISS performance of Fe-Spiro, Fe-Spiro@PPy and Fe-Spiro@PTh.

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Data availability

All of the data supporting the findings of this study are available in the Article and its Supplementary Information. X-ray crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2384930 ((S)-Fe-Spiro@PTh), 2452106 ((R)-Fe-Spiro@PTh), 2384928 ((R)-Fe-Spiro@PPy), 2452104 ((S)-Fe-Spiro@PPy), 2452105 (MIL-88(Fe)@PPy) and 2452103 (MIL-88(Fe)@PTh). These data can be accessed free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

We thank the staff of the BL17B beamline of the National Facility for Protein Science in Shanghai (NFPS) at the Shanghai Synchrotron Radiation Facility for assistance during data collection. This work was financially supported by the National Science Foundation of China (grant nos. 22225111, 22331007 and 52172172), the National Key Basic Research Program of China (grant nos. 2022YFA1503302, 2021YFA1200302, 2021YFA1200402 and 2021YFA1501501), the Key Project of Basic Research of Shanghai (grant no. 22JC1402000), and the Shenzhen Science and Technology Program (grant no. CJGJZD20210408091800002).

Author information

Author notes

  1. These authors contributed equally: Xinfa Chen, Xiaofeng Zhang.

Authors and Affiliations

  1. State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, People’s Republic of China

    Xinfa Chen, Xiaofeng Zhang, Chao Jiang, Wei Gong, Yan Liu & Yong Cui

  2. School of Intelligent Manufacturing, Hunan First Normal University, Changsha, People’s Republic of China

    Can Leng

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  1. Xinfa Chen
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Contributions

Y.C. and Y.L. conceived the idea. X.C., X.Z., C.J. and W.G. designed and performed the MOF synthesis, SCXRD data collection and analysis, and AFM measurements. X.C. performed the NMR, CD, UV–visible, FTIR, Raman, XPS, MALDI-TOF-MS, elemental analysis and thermal gravimetric analyses. X.C. and W.G. advised on the interpretation of results. C.L. performed the TDDFT simulations. Y.C., Y.L., W.G. and X.C. wrote the paper. All authors contributed to the data analysis, discussion and revision of the paper.

Corresponding authors

Correspondence to Yan Liu or Yong Cui.

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Peer review information

Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–67, Tables 1–11, and experimental and X-ray crystallographic details.

Supplementary Crystallographic Data 1

Crystallographic data for (R)-Fe-Spiro@PPy, CCDC 2384928.

Supplementary Crystallographic Data 2

Crystallographic data for (R)-Fe-Spiro@PTh, CCDC 2452106.

Supplementary Crystallographic Data 3

Crystallographic data for (S)-Fe-Spiro@PPy, CCDC 2452104.

Supplementary Crystallographic Data 4

Crystallographic data for (S)-Fe-Spiro@PTh, CCDC 2384930.

Supplementary Crystallographic Data 5

Crystallographic data for MIL-88(Fe)@PPy, CCDC 2452105.

Supplementary Crystallographic Data 6

Crystallographic data for MIL-88(Fe)@PTh.cif, CCDC 2452103.

Supplementary Data 1 (download ZIP )

Source data.

Source data

Source Data Fig. 2 (download XLSX )

Source data for Fig. 2b.

Source Data Fig. 3 (download XLSX )

Source data for Fig. 3b.

Source Data Fig. 4 (download XLSX )

Source data for Fig. 4a–f.

Source Data Fig. 5 (download XLSX )

Source data for Fig. 5b–i.

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Chen, X., Zhang, X., Leng, C. et al. Helical polymer metal–organic framework hybrids. Nat. Synth 5, 46–54 (2026). https://doi.org/10.1038/s44160-025-00909-1

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