Self-assembled poly-catenanes from supramolecular toroidal building blocks

Abstract

Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science1,2. One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking3,4,5,6,7,8,9. This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’10, a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy.

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Fig. 1: Self-assembly of a barbiturated monomer into various supramolecular polymer topologies.
Fig. 2: Supramolecular polymerization protocols.
Fig. 3: Solvent dependence of the catenane yield.
Fig. 4: Nano-polycatenanes.

Data availability

All data supporting the findings of this study are available within the paper and its Supplementary Information files.

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Acknowledgmements

This work was supported by KAKENHI grant number 26102010 and a Grant-in-Aid for Scientific Research on Innovative Areas “π-Figuration” (grant number 26102001) from the Japanese Ministry of Education, Culture, Sports, Science, and Technology (MEXT). This work was also supported by JSPS KAKENHI grant number 19H02760. S.Y. acknowledges financial support from the Murata Science Foundation and the Shorai Foundation for Science and Technology. S.D. and K.A. thank the JSPS for research fellowships P19341 and 17J02520, respectively. G.M.P. acknowledges funding by the Swiss National Science Foundation (SNSF grants IZLIZ2_183336 and 200021_175735) and by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 818776 - DYNAPOL). G.M.P. also acknowledges the computational resources provided by the Swiss National Supercomputing Centre (CSCS) and by CINECA. The SANS experiment at the ISIS facility was allocated under beamtime XB1980292 (https://doi.org/10.5286/ISIS.E.RB1990292-1).

Author information

Affiliations

Authors

Contributions

S.Y. and S.D. designed the project. Y. Kato and S.H. performed most of the experimental work. M.J.H., A.J.S., R.D. and N.M. recorded and simulated the SAXS/SANS data and wrote the SAXS/SANS section of the manuscript. G.M.P., L.P. and C.P. performed the theoretical calculation and wrote the theoretical calculation section of the manuscript. S.Y. and S.D. analysed and explained the experimental data. S.Y. and S.D. prepared the overall manuscript, including figures. All authors, including K.A., A.I., T.S., D.D.P. and Y. Kitamoto, contributed by commenting on the manuscript. The overall project was directed by S.Y.

Corresponding author

Correspondence to Shiki Yagai.

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Extended data figures and tables

Extended Data Fig. 1 Separation of toroids from elongated fibres via thermal reorganization followed by membrane filtration.

a, AFM image of supramolecular polymers obtained by heating a quenched solution of 1 (cT = 1 × 10−4 M) in MCH/CHCl3 (9:1 v:v) at 363 K for 5 min and subsequently cooling to 293 K at a cooling rate of 1.0 K min−1. b, AFM image of supramolecular polymers obtained after passing the resulting solution through a membrane filter with a pore size of 200 nm. The samples were spin-coated onto a HOPG substrate at 293 K. Scale bars, 100 nm.

Extended Data Fig. 2 AFM images of supramolecular polymers obtained in various n-alkanes by single-injection solvent-mixing experiment.

af, AFM images of supramolecular polymers prepared by injecting a 100-μl chloroform solution of 1 (1 × 10−3 M) into 900 μl of n-hexane (a), n-heptane (b), n-octane (c, d), n-nonane (e) or n-decane (f) in one portion. Nano-[n]catenanes with n = 2, 3, 4, 5, 6 are shown by dashed white, blue, green, red and pink circles, respectively. The samples were spin-coated onto a HOPG substrate at 293 K. Scale bars, 100 nm.

Extended Data Fig. 3 AFM images and height profile analysis of nanolympiadane.

a, b, AFM images of nanolympiadane obtained by injecting 100 μl of a chloroform solution of 1 (1 × 10−3 M) into 900 μl of n-octane in one portion. c, AFM height profile analysis of nanolympiadane. Scale bars, 50 nm.

Extended Data Fig. 4 Three-dimensional representations of nanolympiadane and Olympic logo.

a, Three-dimensional arrangement of five toroids in our nanolympiadane on a HOPG surface. b, Three-dimensional representation of five toroids deduced from the two-dimensional representation of the Olympic logo.

Extended Data Fig. 5 Dependence of yields of various supramolecular polymer topologies in different poor solvents on the number of monomer solution injections.

Histogram showing the yield of catenanes (red bars), toroids (green bars) and open-ended coils (blue bars) according to the choice of poor solvent and the number of injections of monomer solution.

Extended Data Fig. 6 Additional AFM images of nano-poly[n]catenanes.

an, AFM images of nano-[6]catenanes (a, b), nano-poly[7]catenanes (c, d), nano-poly[8]catenanes (e), nano-poly[10]catenanes (f, g), nano-poly[11]catenanes (h), nano-poly[12]catenanes (i, j), nano-poly[13]catenanes (k), nano-poly[14]catenanes (l), nano-poly[15]catenanes (m) and nano-poly[18]catenanes (n) obtained by injecting ten portions (one per second) of 10 μl of a chloroform solution of 1 (1 × 10−3 M) into 900 μl of poor solvent. Nano-[6]catenanes (a, b), nano-poly[7]catenanes (c), nano-poly[8]catenanes (e), nano-poly[11]catenanes (h), nano-poly[12]catenanes (j), nano-poly[13]catenanes (k), nano-poly[14]catenanes (l), nano-poly[15]catenanes (m) and nano-poly[18]catenanes (n) were obtained using n-octane as poor solvent. Nano-poly[7]catenanes (d), nano-poly[10]catenanes (f, g) and nano-poly[12]catenanes (i) were obtained when cyclohexane (d, i) and MCH (f, g) were used as poor solvents. The samples were spin-coated onto a HOPG substrate at 293 K. The numbers of interlocked toroids of nano-[n]catenanes and nano-poly[n]catenanes are shown. Scale bars, 50 nm.

Supplementary information

Supplementary Information

This file contains Supplementary Methods and Computational Details, Supplementary Figures 1–13, two Supplementary Discussions, Supplementary Table 1 and Supplementary References.

Supplementary Data 1

The structure of the coarse-grained model of a full rosette (pdb format).

Supplementary Data 2

Force field parameters for the explicit-solvent CG model of a full rosette (itp GROMACS format).

Supplementary Data 3

Force field parameters for the implicit-solvent CG model of a full rosette (itp GROMACS format).

Supplementary Data 4

The structure of the coarse-grained model of a full toroid (pdb format).

Supplementary Video 1

Single-injection solvent mixing experiment. Demonstration of the solvent-mixing experiment for the preparation of kinetic supramolecular polymer species by injecting a 100 μL chloroform solution of 1 (cT = 1 × 10−3 M) into 900 μL of MCH in one portion.

Supplementary Video 2

Ten-injections solvent mixing experiment. Demonstration of the solvent-mixing experiment for the preparation of kinetic supramolecular polymer species by injecting ten portions (one per second) of 10 μL of a chloroform solution of 1 (1 × 10−3 M) into 900 μL of MCH solvent.

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Datta, S., Kato, Y., Higashiharaguchi, S. et al. Self-assembled poly-catenanes from supramolecular toroidal building blocks. Nature 583, 400–405 (2020). https://doi.org/10.1038/s41586-020-2445-z

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