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Self-assembly of chiroptical ionic co-crystals from silver nanoclusters and organic macrocycles

Nature Chemistry volume 17, pages 169–176 (2025)Cite this article

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Abstract

Atomically precise nanoclusters can be assembled into ordered superlattices with unique electronic, magnetic, optical and catalytic properties. The co-crystallization of nanoclusters with functional organic molecules provides opportunities to access an even wider range of structures and properties, but can be challenging to control synthetically. Here we introduce a supramolecular approach to direct the assembly of atomically precise silver nanoclusters into a series of nanocluster‒organic ionic co-crystals with tunable structures and properties. By leveraging non-covalent interactions between anionic silver nanoclusters and cationic organic macrocycles of varying sizes, the orientation of nanocluster surface ligands can be manipulated to achieve in situ resolution of enantiopure nanocluster‒organic ionic co-crystals that feature large chiroptical effects. Beyond chirality, this co-crystal assembly approach provides a promising platform for designing functional solid-state nanomaterials through a combination of supramolecular chemistry and atomically precise nanochemistry.

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Fig. 1: Designing functional NOICs.
Fig. 2: Intermolecular interactions within NOICs.
Fig. 3: The evolution of chirality in NOICs.
Fig. 4: FDCD of NOICs.

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Data availability

Data supporting the findings of this study are available within the Article and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition nos. CCDC 2352972 (NOIC25-2C41C8-A), 2352973 (NOIC25-3C6-L), 2352974 (NOIC25-3C6-R1), 2352975 (NOIC25-3C6-R2), 2352976 (NOIC25-3C6-R3), 2352977 (NOIC25-3C6-R4), 2352978 (NOIC25-3C6-R5), 2352979 (NOIC25-3C7-L), 2352980 (NOIC25-3C7-R), 2352981 (NOIC25-3C8-L), 2352982 (NOIC25-3C8-R), 2342983 (NOIC25-2C61C8-L), 2352984 (NOIC25-2C61C8-R), 2352985 (NOIC25-2C81C6-L), 2352986 (NOIC25-2C81C6-R) and 2352987 (NOIC25-3C3-M). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

We acknowledge support from the Major Research Instrumentation (MRI) Program of the National Science Foundation under NSF award no. 2216066 for crystallography experiments. This work was performed in part at the Harvard University Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network (NNCI), which is supported by the National Science Foundation under NSF award no. ECCS-2025158. We thank the IBS Center for Catalytic Hydrocarbon Functionalizations for computational resources. This research was partially supported by the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator grant awarded to J.A.M. and a National Science Foundation Graduate Research Fellowship awarded to G.J.S.

Author information

Author notes

  1. Yingwei Li

    Present address: Department of Chemistry, University of Hawai‘i at Manoa, Honolulu, HI, USA

  2. These authors contributed equally: Yingwei Li, Grant J. Stec.

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA

    Yingwei Li, Grant J. Stec, Hong Ki Kim, Surendra Thapa, Shao-Liang Zheng & Jarad A. Mason

  2. Center for Nanoscale Systems, Harvard University, Cambridge, MA, USA

    Arthur McClelland

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Contributions

J.A.M., Y.L. and G.J.S. conceived the initial idea. G.J.S. and S.T. synthesized and characterized the organic molecules. Y.L. prepared and characterized the co-crystals. G.J.S. and Y.L. collected X-ray diffraction data and solved the crystal structures with the help of S.-L.Z. G.J.S. and Y.L conducted FDCD measurements with the help of A.M. Y.L. and G.J.S. analysed the FDCD data. H.K.K. and G.J.S performed DFT calculations. Y.L., G.J.S., H.K.K. and J.A.M. wrote the paper, and all authors contributed to editing the paper.

Corresponding author

Correspondence to Jarad A. Mason.

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The authors declare no competing interests.

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

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Extended data

Extended Data Fig. 1 Stability of Ag25 clusters with different counterions.

UV-vis-NIR absorption spectra of a, Ag25(SR)18−PPh4+, b, Ag25(SR)18−TATA3C3+, and c, Ag25(SR)18−TATA3C7+ in CH2Cl2 solution at different time points. Spectra in b and c are offset vertically for clarity.

Source data

Extended Data Fig. 2 Representative optical images of NOIC25−3Cm (m = 3–8).

Scale bar = 100 μm.

Extended Data Fig. 3 Calculations of non-covalent interactions.

“Marionette” interactions (top) and C‒H‧‧‧π interactions (bottom) between a TATA+ ion and a Ag25(SR)18− nanocluster in a, NOIC25−3C6‒R, b, NOIC25−3C7‒L, c, NOIC25−3C7‒R, and d, NOIC25−3C8‒R.

Extended Data Fig. 4 Calculated association energy of TATA+ and Ag25(SR)18−–R.

a, Schematic illustration of rotational analysis of a TATA3C7+ residing on a Ag25(SR)18−–R nanocluster at every 10°. b, Relative E(SCF) energies (black circles) of the TATA3C7+ and Ag25(SR)18−–R pair in NOIC25‒3C7‒R as a function of torsional angle and a fit to the values (red dotted line).

Extended Data Fig. 5 Lattice structures of NOICs with symmetric TATAs.

Structures of a, NOIC25−3C6‒L/R, b, NOIC25−3C7‒L/R and c, NOIC25−3C8‒L/R. In TATA3C8+ (panel c), the three C8 chains are disordered among three conformations (marked in different colors) with occupancies of each disorder type = 0.33 for NOIC25−3C8‒L; the C5‒C8 atoms of the three C8 chains (highlighted in orange) are disordered between two conformations with occupancies of both disorder type I/II = 0.5(3) for NOIC25−3C8‒R. Color codes: light blue = N, blue/magenta/yellow/orange/pink = C in TATA+; purple = Ag, yellow = S, grey = C. Note that H atoms and CH2Cl2 solvent molecules in the crystal structures are omitted for clarity.

Extended Data Fig. 6 Photoluminescence (PL) spectra (linearly polarized).

Linearly polarized photoluminescence spectra for Ag25(SR)18−PPh4+ single crystal (black line), NOIC25−3C7 (maroon line), and TATA3C7+BF4‒ single crystal (magenta line). PL intensities are normalized to the peak maximum. λex = 490 nm.

Source data

Extended Data Fig. 7 Photoluminescence spectra of NOIC25−3C7 (circular polarized).

Averaged photoluminescence spectra of a, NOIC25−3C7‒L crystal #1, b, NOIC25−3C7‒R crystal #1, c, NOIC25−3C7‒L crystal #2, and d, NOIC25−3C7‒R crystal #2 excited by LCP light (left) and RCP light (right), λex = 490 nm. Four spectra obtained at different positions on the same crystal were averaged (solid lines), and shaded regions correspond to ±1 s.d. e, FDCD IL–IR of NOIC25−3C7‒L (#1 and #2) and NOIC25−3C7‒R (#1 and #2), and f, corresponding FDCD gabs-lum.

Source data

Extended Data Fig. 8 Photoluminescence spectra of NOIC25−3C7 (circular polarized).

Averaged photoluminescence spectra of a, NOIC25−3C7‒L crystal #3, b, NOIC25−3C7‒R crystal #3, c, NOIC25−3C7‒L crystal #4, and d, NOIC25−3C7‒R crystal #4 excited by LCP light (left) and RCP light (right), λex = 490 nm. Four spectra obtained at different positions on the same crystal were averaged (solid lines), and shaded regions correspond to ±1 s.d. e, FDCD IL–IR of NOIC25−3C7‒L (#3 and #4) and NOIC25−3C7‒R (#3 and #4), and f, corresponding FDCD gabs-lum.

Source data

Extended Data Fig. 9 Effect of intermolecular exciton coupling on the dissymmetry factor.

a, A one-dimensional chain of TATA+ molecules with fixed 20.6 Å spacing and a variable angle, θ, between the transition dipole \(\mathop{{\rm{\mu }}}\limits^{ \rightharpoonup }\) (red) and vector connecting TATA+ centers (blue). b, Rotational strength vs. number of TATAs in the one-dimensional chain for TATA+ molecules rotated 10° clockwise (θ = 100°, red) or 10° counterclockwise (θ = 80°, blue) away from perpendicular. c, Periodic variation of dissymmetry factor as the angle between the intermolecular vector and transition dipole vector changes. The simulated dissymmetry factor corresponding to the experimental θ is indicated in pink.

Extended Data Fig. 10 Effect of crystal orientation on FDCD of NOIC25−3C7‒L/R.

FDCD gabs-lum of a, NOIC25−3C7‒R and b, NOIC25−3C7‒L measured at different crystal rotation angles relative to the incident excitation light. Average values across all rotation angles are shown as solid lines, and shaded regions correspond to ±1 standard deviation. The excitation wavelength was 490 nm for all measurements.

Source data

Supplementary information

Supplementary Information (download PDF )

Further Methods and discussion, and Supplementary Figs. 1–17 and Tables 1–18.

Supplementary Data 1

Crystallographic data for NOIC25-2C41C8-A (CCDC no. 2352972).

Supplementary Data 2

Crystallographic data for NOIC25-3C6-L (CCDC no. 2352973).

Supplementary Data 3

Crystallographic data for NOIC25-3C6-R1 (CCDC no. 2352974).

Supplementary Data 4

Crystallographic data for NOIC25-3C6-R2 (CCDC no. 2352975).

Supplementary Data 5

Crystallographic data for NOIC25-3C6-R3 (CCDC no. 2352976).

Supplementary Data 6

Crystallographic data for NOIC25-3C6-R4 (CCDC no. 2352977).

Supplementary Data 7

Crystallographic data for NOIC25-3C6-R5 (CCDC no. 2352978).

Supplementary Data 8

Crystallographic data for NOIC25-3C7-L (CCDC no. 2352979).

Supplementary Data 9

Crystallographic data for NOIC25-3C7-R (CCDC no. 2352980).

Supplementary Data 10

Crystallographic data for NOIC25-3C8-L (CCDC no. 2352981).

Supplementary Data 11

Crystallographic data for NOIC25-3C8-R (CCDC no. 2352982).

Supplementary Data 12

Crystallographic data for NOIC25-2C61C8-L (CCDC no. 2352983).

Supplementary Data 13

Crystallographic data for NOIC25-2C61C8-R (CCDC no. 2352984).

Supplementary Data 14

Crystallographic data for NOIC25-2C81C6-L (CCDC no. 2352985).

Supplementary Data 15

Crystallographic data for NOIC25-2C81C6-R (CCDC no. 2352986).

Supplementary Data 16

Crystallographic data for NOIC25-3C3-M (CCDC no. 2352987).

Supplementary Data 17 (download XLSX )

Statistical source data for Supplementary Figs. 1 and 13–17.

Source data

Source Data Fig. 4 (download XLSX )

Statistical source data for Fig. 4.

Source Data Extended Data Fig. 1 (download XLSX )

Statistical source data for Extended Data Fig. 1.

Source Data Extended Data Fig. 6 (download XLSX )

Statistical source data for Extended Data Fig. 6.

Source Data Extended Data Fig. 7 (download XLSX )

Statistical source data for Extended Data Fig. 7.

Source Data Extended Data Fig. 8 (download XLSX )

Statistical source data for Extended Data Fig. 8.

Source Data Extended Data Fig. 10 (download XLSX )

Statistical source data for Extended Data Fig. 10.

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Li, Y., Stec, G.J., Kim, H.K. et al. Self-assembly of chiroptical ionic co-crystals from silver nanoclusters and organic macrocycles. Nat. Chem. 17, 169–176 (2025). https://doi.org/10.1038/s41557-024-01696-6

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