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Solvent-free autocatalytic supramolecular polymerization

Nature Materials volume 21, pages 253–261 (2022)Cite this article

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Abstract

Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.

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Fig. 1: Autocatalysis driven by solvent-free supramolecular polymerization.
Fig. 2: Characterization of SF-ASP.
Fig. 3: Characterization of [HPCC4]CF obtained by SF-ASP.
Fig. 4: Sequence and orientation controls of crystalline fibres obtained by SF-ASP.

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Data availability

Data generated or analysed during this study are provided as source data or included in the Supplementary Information. Further data are available from the corresponding authors on request. Source data are provided with this paper.

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Acknowledgements

We thank C. Zhang (RIKEN) and H. Gong (The University of Tokyo) for their generous experimental support. This work was financially supported by the Japan Society for the Promotion of Science (JSPS) through its Grants-in-Aid for Specially Promoted Research (25000005) on ‘Physically Perturbed Assembly for Tailoring High-Performance Soft Materials with Controlled Macroscopic Structural Anisotropy’ for T.A. D.M. thanks JSPS for a Young Scientist A (grant no. 15H05487) and Coordination Asymmetry (grant no. JP17H05394).

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  1. Zhen Chen

    Present address: Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, China

Authors and Affiliations

  1. RIKEN Center for Emergent Matter Science, Wako, Saitama, Japan

    Zhen Chen, Yukinaga Suzuki, Ayumi Imayoshi, Xiaofan Ji, Kotagiri Venkata Rao, Yuki Omata, Daigo Miyajima, Emiko Sato, Atsuko Nihonyanagi & Takuzo Aida

  2. Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan

    Zhen Chen, Yukinaga Suzuki & Takuzo Aida

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Contributions

Z.C. designed and preformed all experiments. Y.S., A.I. and X.J. designed and assisted partial experiments and analysed the data. K.V.R., Y.O., E.S. and A.N. performed partial synthetic experiments. D.M. and T.A. conceived the project and codesigned the experiments. Z.C., D.M. and T.A. analysed the data and wrote the paper.

Corresponding authors

Correspondence to Daigo Miyajima or Takuzo Aida.

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Peer review information Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Tables 1–4, Videos 1 and 2 and Methods.

Supplementary Video 1

SF-ASP using PNC4 sandwiched between glass plates on heating at 160 °C, where the green-coloured thin fibres form.

Supplementary Video 2

SF-ASP using PNC4 in the presence of crystalline fibres of [HPCC4]CF as the seed sandwiched between CYTOP-coated glass plates on heating at 160 °C for 5 h, where the crystalline fibres elongate immediately.

Source data

Source Data Fig. 2

a, Time-dependent absorption changes at 700 nm of HPCs. b, Temperature effect on the yields of HPCC4. d, MALDI–TOF mass spectrometry data.

Source Data Fig. 3

b, PXRD data. f, Polarized infrared data.

Source Data Fig. 4

a, Time-dependent absorption changes at 700 nm of MPCC4.

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Chen, Z., Suzuki, Y., Imayoshi, A. et al. Solvent-free autocatalytic supramolecular polymerization. Nat. Mater. 21, 253–261 (2022). https://doi.org/10.1038/s41563-021-01122-z

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