DNA has long been used as a template for the construction of helical assemblies of inorganic nanoparticles1,2,3,4,5. For example, gold nanoparticles decorated with DNA (or with peptides) can create helical assemblies6,7,8,9. But without such biological ligands, helices are difficult to achieve and their mechanism of formation is challenging to understand10,11. Atomically precise nanoclusters that are protected by ligands such as thiolate12,13 have demonstrated hierarchical structural complexity in their assembly at the interparticle and intraparticle levels, similar to biomolecules and their assemblies14. Furthermore, carrier dynamics can be controlled by engineering the structure of the nanoclusters15. But these nanoclusters usually have isotropic structures16,17 and often assemble into commonly found supercrystals18. Here we report the synthesis of homodimeric and heterodimeric gold nanoclusters and their self-assembly into superstructures. While the homodimeric nanoclusters form layer-by-layer superstructures, the heterodimeric nanoclusters self-assemble into double- and quadruple-helical superstructures. These complex arrangements are the result of two different motif pairs, one pair per monomer, where each motif bonds with its paired motif on a neighbouring heterodimer. This motif pairing is reminiscent of the paired interactions of nucleobases in DNA helices. Meanwhile, the surrounding ligands on the clusters show doubly or triply paired steric interactions. The helical assembly is driven by van der Waals interactions through particle rotation and conformational matching. Furthermore, the heterodimeric clusters have a carrier lifetime that is roughly 65 times longer than that of the homodimeric clusters. Our findings suggest new approaches for increasing complexity in the structural design and engineering of precision in supercrystals.
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The cif files for the crystal structures of Au29(SAdm)19 and Au30(SAdm)18, and videos to show the double or quadruple helices in the Au29(SAdm)19 supercrystal, are provided as Supplementary Information with this paper. The cif files can be found at the Cambridge Crystallographic Data Centre (CCDC; https://www.ccdc.cam.ac.uk) under accession numbers 2072909 for Au29(SAdm)19 and 2072908 for Au30(SAdm)18.
Srivastava, S. et al. Light-controlled self-assembly of semiconductor nanoparticles into twisted ribbons. Science 327, 1355–1359 (2010).
Singh, G. et al. Self-assembly of magnetite nanocubes into helical superstructures. Science 345, 1149–1153 (2014).
Shenhar, R. & Rotello, V. M. Nanoparticles: scaffolds and building blocks. Acc. Chem. Res. 36, 549–561 (2003).
Gao, Y. & Tang, Z. Design and application of inorganic nanoparticle superstructures: current status and future challenges. Small 7, 2133–2146 (2011).
Saleh, L. M. A., Dziedzic, R. & Spokoyny, A. M. An inorganic twist in nanomaterials: making an atomically precise double helix. ACS Cent. Sci. 2, 685–686 (2016).
Sharma, J. et al. Control of self-assembly of DNA tubules through integration of gold nanoparticles. Science 323, 112–116 (2009).
Kuzyk, A. et al. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 483, 311–314 (2012).
Chen, C.-L., Zhang, P. & Rosi, N. L. A new peptide-based method for the design and synthesis of nanoparticle superstructures: construction of highly ordered gold nanoparticle double helices. J. Am. Chem. Soc. 130, 13555–13557 (2008).
Shen, X. et al. Rolling up gold nanoparticle-dressed DNA origami into three-dimensional plasmonic chiral nanostructures. J. Am. Chem. Soc. 134, 146–149 (2012).
Berl, V., Huc, I., Khoury, R. G., Krische, M. J. & Lehn, J.-M. Interconversion of single and double helices formed from synthetic molecular strands. Nature 407, 720–723 (2000).
Engelkamp, H. & Middelbeek, S. & Nolte, R. J. M. Self-assembly of disk-shaped molecules to coiled-coil aggregates with tunable helicity. Science 284, 785–788 (1999).
Jin, R., Zeng, C., Zhou, M. & Chen, Y. Atomically precise colloidal metal nanoclusters and nanoparticles: fundamentals and opportunities. Chem. Rev. 116, 10346–10413 (2016).
Li, Y., Higaki, T., Du, X. & Jin, R. Chirality and surface bonding correlation in atomically precise metal nanoclusters. Adv. Mater. 32, 1905488 (2020).
Zeng, C., Chen, Y., Kirschbaum, K., Lambright, K. J. & Jin, R. Emergence of hierarchical structural complexities in nanoparticles and their assembly. Science 354, 1580–1584 (2016).
Zhou, M. et al. Three-orders-of-magnitude variation of carrier lifetimes with crystal phase of gold nanoclusters. Science 364, 279–282 (2019).
Zhu, M., Aikens, C. M., Hollander, F. J., Schatz, G. C. & Jin, R. Correlating the crystal structure of a thiol-protected Au25 cluster and optical properties. J. Am. Chem. Soc. 130, 5883–5885 (2008).
Desireddy, A. et al. Ultrastable silver nanoparticles. Nature 501, 399–402 (2013).
Macfarlane, R. J. et al. Nanoparticle superlattice engineering with DNA. Science 334, 204–208 (2011).
Li, Y. & Jin, R. Seeing ligands on nanoclusters and in their assemblies by X-ray crystallography: atomically precise nanochemistry and beyond. J. Am. Chem. Soc. 142, 13627–13644 (2020).
Gan, Z. et al. The fourth crystallographic closest packing unveiled in the gold nanocluster crystal. Nat. Commun. 8, 14739 (2017).
Gu, H., Zheng, R., Zhang, X. & Xu, B. Facile one-pot synthesis of bifunctional heterodimers of nanoparticles: a conjugate of quantum dot and magnetic nanoparticles. J. Am. Chem. Soc. 126, 5664–5665 (2004).
Choi, J. et al. Biocompatible heterostructured nanoparticles for multimodal biological detection. J. Am. Chem. Soc. 128, 15982–15983 (2006).
Brown, L. V., Sobhani, H., Lassiter, J. B., Nordlander, P. & Halas, N. J. Heterodimers: plasmonic properties of mismatched nanoparticle pairs. ACS Nano 4, 819–832 (2010).
Buck, M. R., Bondi, J. F. & Schaak, R. E. A total-synthesis framework for the construction of high-order colloidal hybrid nanoparticles. Nat. Chem. 4, 37–44 (2012).
Zhu, H. et al. Self-assembly of quantum dot–gold heterodimer nanocrystals with orientational order. Nano Lett. 18, 5049–5056 (2018).
Xiong, L., Peng, B., Ma, Z., Wang, P. & Pei, Y. A ten-electron (10e) thiolate-protected Au29(SR)19 cluster: structure prediction and a ‘gold-atom insertion, thiolate-group elimination’ mechanism. Nanoscale 9, 2895–2902 (2017).
Chen, Y. et al. Isomerism in Au28(SR)20 nanocluster and stable structures. J. Am. Chem. Soc. 138, 1482–1485 (2016).
Li, Y. et al. A correlated series of Au/Ag nanoclusters revealing the evolutionary patterns of asymmetric Ag doping. J. Am. Chem. Soc. 140, 14235–14243 (2018).
Higaki, T. et al. Controlling the atomic structure of Au30 nanoclusters by a ligand-based strategy. Angew. Chem. Int. Edn 55, 6694–6697 (2016).
Zhou, M. et al. Three-stage evolution from nonscalable to scalable optical properties of thiolate-protected gold nanoclusters. J. Am. Chem. Soc. 141, 19754–19764 (2019).
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. 42, 339–341 (2009).
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment—Olex2 dissected. Acta Crystallogr. A 71, 59–75 (2015).
Sheldrick, G. M. SHELXT—integrated space-group and crystal-structure determination. Acta Crystallogr. A 71, 3–8 (2015).
Y.L. and R.J. thank T.-Y. Luo for help in analysing crystal data. R.J. acknowledges financial support from the US National Science Foundation (NSF; grant DMR-1808675). H.W. acknowledges financial support from US Air Force Office of Scientific Research (AFOSR) award FA9550-17-1-0099. Y.S. acknowledges the startup.
The authors declare no competing interests.
Peer review information Nature thanks the anonymous reviewer(s) for their contribution to the peer review of this work.
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Extended data figures and tables
Extended Data Fig. 1 Separation by TLC and characterization of Au29(SAdm)19 and Au30(SAdm)18 nanoclusters.
a, Separation of multiple Au-SAdm nanoclusters by TLC. b, Absorption spectra of heterodimeric Au29(SAdm)19 and homodimeric Au30(SAdm)18 nanoclusters on a photon energy scale. The bandgaps are determined to be 1.45 eV and 1.25 eV, respectively. c, Isotope peaks corresponding to [Au30(SAdm)18]2+ and [Au30(SAdm)18]+ (red lines), [Au29(SAdm)19]2+, [Au29(SAdm)19]+, [Au29(SAdm)19Ag]2+ and [Au29(SAdm)19Ag]+ (blue lines). The experimental isotopic patterns match well with the calculated ones (black lines). Note that the 2+ and 1+ charges are due to the ionization in ESI, and are not the native charge states of the nanoclusters. In addition, an Ag cation can be picked up by Au29(SAdm)19 during ESI-MS analysis owing to the existence of Ag+ in the ion source.
a, Au30(SR)18; b Au28(SR)20; c, Au29(SR)19.
a, The triply paired ligands associated with the matching motif pairs on two neighbouring enantiomers—that is, E1C1–E2C3 and E1C3–E2C1—with interacting ligands’ carbons marked in orange (for C1) and red (for C3). b, The doubly paired ligands associated with the matching motif pairs on two neighbouring enantiomers—E1L3–E2L1 and E1L1–E2L3—with interacting ligands’ carbons marked in light blue (for L1) and green (for L3). In other colours: blue/cyan, Au in different enantiomers; yellow, S; grey, C; white, H.
a, Self-assembly of Au30(SAdm)18 nanoclusters in the superlattice. b, The neighbouring enantiomers approach each other by matching their L3 staple motifs, with doubly paired and triply paired ligand interactions between the two enantiomers.
a, Self-assembly of Au21(SAdm)15 nanoclusters in the superlattice. b, Ligand interactions between two enantiomers. We made this figure using crystal data from ref. 28.
a, Self-assembly of Au20Ag1(SAdm)15 nanoclusters in the superlattice. b, Ligand interactions between two enantiomers. We made this figure using crystal data from ref. 28.
a, Self-assembly of Au19Ag4(SAdm)15 nanoclusters in the superlattice. b, Ligand interactions between two enantiomers. We made this figure using crystal data from ref. 28.
a, Self-assembly of Au23–xAgx(SAdm)15 nanoclusters (x is approximately 7) in the superlattice. b, Ligand interactions between two enantiomers. We made this figure using crystal data from ref. 28.
Extended Data Fig. 9 Maps of picosecond transient absorption data and kinetic traces of Au29(SAdm)19 and Au30(SAdm)18 nanoclusters, with NIR photoluminescence of Au29(SAdm)19.
a–c, Au29(SAdm)19 (kinetic traces probed at 500 nm (blue), 630 nm (red) and 700 nm (green)). d–f, Au30(SAdm)18 (kinetic traces probed at 600 nm (blue), 700 nm (red) and 540 nm (green)). Both nanoclusters were excited at 400 nm. g, Emission spectra (λex = 430 nm) for a solution (red; toluene solvent), film (blue; drop casting from a concentrated solution) and supercrystals (brown) of Au29(SAdm)19. Inset, photograph of Au29(SAdm)19 supercrystals under optical microscopy.
CheckCif1 report for the crystal structure of Au29(SAdm)19.
CheckCif2 report for the crystal structure of Au30(SAdm)18.
The double helix of Au29(SAdm)19 NCs in right-handed rotation.
The double helix of Au29(SAdm)19 NCs in left-handed rotation.
The quadruple helix of Au29(SAdm)19 NCs in right-handed rotation.
The quadruple helix of Au29(SAdm)19 NCs in left-handed rotation.
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Li, Y., Zhou, M., Song, Y. et al. Double-helical assembly of heterodimeric nanoclusters into supercrystals. Nature 594, 380–384 (2021). https://doi.org/10.1038/s41586-021-03564-6
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