Symmetry Breaking in Chiral Gold Nanoclusters by Ansa-Metallamacrocycles Strain

Abstract

Chiral nanomaterials have recently stimulated significant interest in both fundamental research and practical applications (e.g., nanoprobes for biomolecular recognition). However, achieving chiral nanoclusters is still a major challenge. Herein, we report an effective strategy that affords achiral diphosphine ligand-protected, chiral Au₁₁ nanoclusters. Synchrotron radiation X-ray diffraction solves the chiral structure of Au₁₁(dppp)₅Cl₃ (dppp = 1,3-bis(diphenylphosphino)propane) and further reveals that the critical feature of bidentate binding of diphosphine induces the unique ansa-metallamacrocycle pattern (i.e., the “Au─P─CH₂CH₂CH₂─P─Au” staple). All the possible ansa-metallamacrocycle patterns are transferred to the most robust pattern by “ligand confinement,” giving rise to the chiral enantiomers. Using Density Functional Theory (DFT), we show that the chirality can emerge due to the low energy barriers facilitating the transformation of the symmetric Au₁₁ core into the corresponding asymmetric chiral cluster, driven by a favorable fit of ligand bridges. This new type of chiral nanomaterial holds promise in chiral sensing/recognition and enantioselective applications.

Keywords

Au₁₁ / chirality / gold nanoclusters / metallomacrocycle

References

[1] M. M. Zhang, X. Y. Dong, Z. Y. Wang, et al., “Alkynyl-Stabilized Superatomic Silver Clusters Showing Circularly Polarized Luminescence,” Journal of the American Chemical Society 143 (2021): 6048–6053.

[2] G. Deng, S. Malola, J. Yan, et al., “From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au₁₃Cu₂ Nanoclusters,” Angewandte Chemie International Edition 57 (2018): 3421–3425.

[3] C. Zeng, Y. Chen, K. Kirschbaum, K. J. Lambright, and R. Jin, “Emergence of Hierarchical Structural Complexities in Nanoparticles and Their Assembly,” Science 354 (2016): 1580–1584.

[4] Y. L. Xie, W. H. Fang, and J. Zhang, “Aggregation of Titanium-Oxo Clusters,” Aggregate 5 (2024): e506.

[5] S. T. Wang, Y. J. Liu, C. C. Feng, W. H. Fang, and J. Zhang, “The Largest Aluminum Molecular Rings: Phenol-Thermal Synthesis, Photoluminescence, and Optical Limiting,” Aggregate 4 (2023): e264.

[6] J. Fang, B. Zhang, Q. Yao, Y. Yang, J. Xie, and N. Yan, “Recent Advances in the Synthesis and Catalytic Applications of Ligand-Protected, Atomically Precise Metal Nanoclusters,” Coordination Chemistry Reviews 322 (2016): 1–29.

[7] R. Jin, G. Li, S. Sharma, Y. Li, and X. Du, “Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters With Crystallographic Structures,” Chemical Reviews 121 (2021): 567–648.

[8] J. Q. Wang, Z. J. Guan, W. D. Liu, Y. Yang, and Q. M. Wang, “Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters,” Journal of the American Chemical Society 141 (2019): 2384–2390.

[9] X. Kang and M. Z. Zhu, “Intra-Cluster Growth Meets Inter-Cluster Assembly: The Molecular and Supramolecular Chemistry of Atomically Precise Nanoclusters,” Coordination Chemistry Reviews 394 (2019): 1–38.

[10] K. Konishi, M. Iwasaki, and Y. Shichibu, “Phosphine-Ligated Gold Clusters With Core + exo Geometries: Unique Properties and Interactions at the Ligand–Cluster Interface,” Accounts of Chemical Research 51 (2018): 3125–3133.

[11] Z. Wu and R. Jin, “Exclusive Synthesis of Au₁₁(PPh₃)₈Br₃ Against the Cl Analogue and the Electronic Interaction Between Cluster Metal Core and Surface Ligands,” Chemistry – A European Journal 19 (2013): 201.

[12] C. E. Briant, B. R. C. Theobald, J. W. White, L. K. Bell, D. M. P. Mingos, and A. J. Welch, “Synthesis and X-Ray Structural Characterization of the Centred Icosahedral Gold Cluster Compound [Au₁₃(PMe₂Ph)₁₀Cl₂](PF6)₃; the Realization of a Theoretical Prediction,” Chemical Communications 5 (1981): 201–202.

[13] Y. Shichibu, K. Suzuki, and K. Konishi, “Facile Synthesis and Optical Properties of Magic-Number Au₁₃ Clusters,” Nanoscale 4 (2012): 4125–4129.

[14] J. Nishigaki, R. Tsunoyama, H. Tsunoyama, et al., “A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster,” Journal of the American Chemical Society 134 (2012): 14295–14297.

[15] Y. Shichibu, Y. Negishi, T. Watanabe, N. K. Chaki, H. Kawaguchi, and T. Tsukuda, “Biicosahedral Gold Clusters [Au₂₅(PPh₃)₁₀(SC_nH_2n+1)₅Cl₂]²⁺ (n = 2−18): A Stepping Stone to Cluster-Assembled Materials,” Journal of Physical Chemistry C 111 (2007): 7845–7847.

[16] L. Yang, H. Cheng, Y. Jiang, et al., “In Situ Studies on Controlling an Atomically-Accurate Formation Process of Gold Nanoclusters,” Nanoscale 7 (2015): 14452–14459.

[17] W. D. Liu, J. Q. Wang, S. F. Yuan, X. Chen, and Q. M. Wang, “Chiral Superatomic Nanoclusters Ag47 Induced by the Ligation of Amino Acids,” Angewandte Chemie International Edition 60 (2021): 11430–11435.

[18] X. He, Y. Wang, H. Jiang, and L. Zhao, “Structurally Well-Defined Sigmoidal Gold Clusters: Probing the Correlation Between Metal Atom Arrangement and Chiroptical Response,” Journal of the American Chemical Society 138 (2016): 5634–5643.

[19] K. R. Krishnadas, L. Sementa, M. Medves, et al., “Chiral Functionalization of an Atomically Precise Noble Metal Cluster: Insights Into the Origin of Chirality and Photoluminescence,” ACS Nano 14 (2020): 9687–9700.

[20] J. Yan, H. Su, H. Yang, et al., “Asymmetric Synthesis of Chiral Bimetallic [Ag₂₈Cu₁₂(SR)₂₄]⁴⁻ Nanoclusters via Ion Pairing,” Journal of the American Chemical Society 138 (2016): 12751–12754.

[21] S. Knoppe, I. Dolamic, A. Dass, and T. Burgi, “Separation of Enantiomers and CD Spectra of Au₄₀(SCH₂CH₂Ph)₂₄: Spectroscopic Evidence for Intrinsic Chirality,” Angewandte Chemie International Edition 51 (2012): 7589–7591.

[22] I. Dolamic, S. Knoppe, A. Dass, and T. Burgi, “First Enantioseparation and Circular Dichroism Spectra of Au₃₈ Clusters Protected by Achiral Ligands,” Nature Communications 3 (2012): 798.

[23] L. Y. Yao and V. W. Yam, “Diphosphine-Stabilized Small Gold Nanoclusters: From Crystal Structure Determination to Ligation-Driven Symmetry Breaking and Anion Exchange Properties,” Journal of the American Chemical Society 138 (2016): 15736–15742.

[24] S. M. Mullins, H. C. Weissker, R. Sinha-Roy, et al., “Chiral Symmetry Breaking Yields the I-Au₆₀ Perfect Golden Shell of Singular Rigidity,” Nature Communications 9 (2016): 3352.

[25] A. Sanchez-Castillo, C. Noguez, and I. L. Garzon, “On the Origin of the Optical Activity Displayed by Chiral-Ligand-Protected Metallic Nanoclusters,” Journal of the American Chemical Society 132 (2010): 1504–1505.

[26] L. Riccardi, F. De Biasi, M. De Vivo, T. Burgi, F. Rastrelli, and G. Salassa, “Dynamic Origin of Chirality Transfer Between Chiral Surface and Achiral Ligand in Au₃₈ Clusters,” ACS Nano 13 (2019): 7127–7134.

[27] J. J. Pelayo, R. L. Whetten, and I. L. Garzón, “Geometric Quantification of Chirality in Ligand-Protected Metal Clusters,” Journal of Physical Chemistry C 119 (2015): 28666–28678.

[28] J. Zhang, Y. Zhou, K. Zheng, et al., “Diphosphine-Induced Chiral Propeller Arrangement of Gold Nanoclusters for Singlet Oxygen Photogeneration,” Nano Research 11 (2018): 5787–5798.

[29] M. McPartlin, R. Mason, and L. Malatesta, “Novel Cluster Complexes of Gold(0)–Gold(I),” Journal of the Chemical Society D: Chemical Communications 7 (1969): 334.

[30] X. K. Wan, S. F. Yuan, Z. W. Lin, and Q. M. Wang, “A Chiral Gold Nanocluster Au₂₀ Protected by Tetradentate Phosphine Ligands,” Angewandte Chemie International Edition 53 (2014): 2923–2926.

[31] R. Q. Chen, S. T. Wang, Y. J. Liu, J. Zhang, and W. H. Fang, “Assembly of Homochiral Aluminum Oxo Clusters for Circularly Polarized Luminescence,” Journal of the American Chemical Society 146 (2024): 7524–7532.

[32] J. Zhang, Y. Huang, G. Li, and Y. Wei, “Recent Advances in Alkoxylation Chemistry of Polyoxometalates: From Synthetic Strategies, Structural Overviews to Functional Applications,” Coordination Chemistry Reviews 378 (2019): 395–414.

[33] J. M. M. Smits, J. J. Bour, F. A. Vollenbroek, and P. T. Beurskens, “Preparation and X-Ray Structure Determination of [Pentakis{1,3-bis(Diphenylphosphino)Propane}] Undecagoldtris(Thiocyanate), [Au₁₁{PPh₂C₃H₆PPh₂}₅](SCN)₃,” Journal of Crystallographic and Spectroscopic Research 13 (1983): 355–363.

[34] R. Jin, C. Zeng, M. Zhou, and Y. Chen, “Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities,” Chemical Reviews 116 (2016): 10346–10413.

[35] C. Zeng, Y. Chen, A. Das, and R. Jin, “Transformation Chemistry of Gold Nanoclusters: From One Stable Size to Another,” Journal of Physical Chemistry Letters 6 (2015): 2976–2986.

[36] L. C. McKenzie, T. O. Zaikova, and J. E. Hutchison, “Structurally Similar Triphenylphosphine-Stabilized Undecagolds, Au₁₁(PPh₃)₇Cl₃ and [Au₁₁(PPh₃)₈Cl₂]Cl, Exhibit Distinct Ligand Exchange Pathways With Glutathione,” Journal of the American Chemical Society 136 (2014): 13426–13435.

[37] S. Takano and T. Tsukuda, “Amplification of the Optical Activity of Gold Clusters by the Proximity of BINAP,” Journal of Physical Chemistry Letters 7 (2016): 4509–4513.

[38] H. Qian, W. T. Eckenhoff, Y. Zhu, T. Pintauer, and R. Jin, “Total Structure Determination of Thiolate-Protected Au₃₈ Nanoparticles,” Journal of the American Chemical Society 132 (2010): 8280–8281.

[39] B. S. Gutrath, U. Englert, Y. Wang, and U. Simon, “A Missing Link in Undecagold Cluster Chemistry: Single-Crystal X-Ray Analysis of [Au₁₁(PPh₃)₇Cl₃],” European Journal of Inorganic Chemistry 2013 (2013): 2002–2006.

[40] C. Liu, H. Abroshan, C. Yan, G. Li, and M. Haruta, “One-Pot Synthesis of Au₁₁(PPh₂Py)₇ Br₃ for the Highly Chemoselective Hydrogenation of Nitrobenzaldehyde,” ACS Catalysis 6 (2016): 92–99.

[41] G. Li, H. Abroshan, C. Liu, et al., “Tailoring the Electronic and Catalytic Properties of Au₂₅ Nanoclusters via Ligand Engineering,” ACS Nano 10 (2016): 7998–8005.

[42] A. Das, C. Liu, C. Zeng, et al., “Cyclopentanethiolato-Protected Au₃₆(SC₅H₉)₂₄ Nanocluster: Crystal Structure and Implications for the Steric and Electronic Effects of Ligand,” Journal of Physical Chemistry A 118 (2014): 8264–8269.

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2025 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.