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Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration

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Abstract

In this study, 1,2-bis(diphenylphosphino)ethane (dppe) ligands are used to synthesize gold nanoclusters with an icosahedral Au13 core. The nanoclusters are characterized and formulated as [Au13(dppe)5Cl2]Cl3 using synchrotron radiation X-ray diffraction, UV/Vis absorption spectroscopy, electrospray ionization mass spectrometry, and density functional theory (DFT) calculations. The bidentate feature of dppe ligands and the positions of coordinating surface gold atoms induce a helical arrangement that forms a propeller-like structure, which reduces the symmetry of the gold nanocluster to C1. Therefore, dppe ligands perform as a directing agent to create chiral an ansa metallamacrocycle [Au13(dppe)5Cl2]3+ nanocluster, as confirmed by simulated electronic circular dichroism spectrum. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the [Au13(dppe)5Cl2]3+ cluster is determined as approx. 1.9 eV, and further confirmed by ultraviolet photoemission spectroscopy analysis and DFT simulation. Furthermore, the photoactivity of [Au13(dppe)5Cl2]3+ is investigated, with the nanocluster shown to possess near-infrared photoluminescence properties, which can be employed for 1O2 photogeneration. The quantum yield of 1O2 photogeneration using the [Au13(dppe)5Cl2]3+ nanocluster is up to 0.71, which is considerably higher than those of anthracene (an organic dye), and Au25 and Au38 nanoclusters.

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Acknowledgements

G. L. acknowledges financial supports by the fund of the National Natural Science Foundation of China (No. 21701168) and the Liaoning Natural Science Foundation (No. 20170540897), and beamline BL14B (Shanghai Synchrotron Radiation Facility) for providing the beam time. A portion of this report was prepared as an account of work sponsored by an agency of the United States Government (D. R. K.). Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights.

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  1. Jiangwei Zhang and Yang Zhou contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Jiangwei Zhang, Yang Zhou, Kai Zheng & Gao Li

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Yang Zhou

  3. SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, California, 94305, USA

    Hadi Abroshan

  4. National Energy Technology Laboratory (NETL), United States Department of Energy, Pittsburgh, Pennsylvania, 15236, USA

    Douglas R. Kauffman

  5. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Junliang Sun

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  1. Jiangwei Zhang
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Correspondence to Gao Li.

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Zhang, J., Zhou, Y., Zheng, K. et al. Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration. Nano Res. 11, 5787–5798 (2018). https://doi.org/10.1007/s12274-017-1935-2

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