Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (1): 1-6.DOI: 10.6023/A21110499 Previous Articles     Next Articles



许道兰a,b, 杨颖a,b, 范文涛b,c,a, 何宗兵a,b, 邹家丰a,b, 冯磊a,b, 李漫波a,b,*(), 伍志鲲a,b,*()   

  1. a安徽大学 物质科学与信息技术研究院 合肥 230601
    b中国科学院固体物理研究所 中国科学院材料物理重点实验室 安徽省纳米材料与技术重点实验室中国科学院纳米卓越中心 中国科学院合肥物质科学研究院 合肥 230031
    c中国科学技术大学 合肥 230026
  • 投稿日期:2021-11-05 发布日期:2021-11-17
  • 通讯作者: 李漫波, 伍志鲲
  • 作者简介:
    †These authors contributed equally to this work.
  • 基金资助:
    项目受国家自然科学基金(92061110); 项目受国家自然科学基金(21925303); 项目受国家自然科学基金(21771186); 项目受国家自然科学基金(21829501); 项目受国家自然科学基金(21222301); 项目受国家自然科学基金(21171170); 项目受国家自然科学基金(21528303); 合肥微尺度物质科学国家研究中心(KF2020102); 安徽大学(以及配备ConfotecTM MR520荧光/拉曼光谱仪)(S020118002/113); 中国科学院合肥研究院院长基金(BJPY2019A02); 中科院合肥物质科学研究院“十三五”规划重点支持项目(KP-2017-16); 中国科学院合肥科学中心协同创新项目(2020HSC-CIP005)

Single, Self-Born RP-Au-PR Motif Boosts 19-Fold Photoluminescence Quantum Yield of Metal Nanocluster

Daolan Xua,b, Ying Yanga,b, Wentao Fanb,c,a, Zongbing Hea,b, Jiafeng Zoua,b, Lei Fenga,b, Man-Bo Lia,b(), Zhikun Wua,b()   

  1. aInstitute of Physical Science and Information Technology, Anhui University, Hefei 230601, China
    bKey Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
    cUniversity of Science and Technology of China, Hefei 230026, China
  • Received:2021-11-05 Published:2021-11-17
  • Contact: Man-Bo Li, Zhikun Wu
  • Supported by:
    National Natural Science Foundation of China(92061110); National Natural Science Foundation of China(21925303); National Natural Science Foundation of China(21771186); National Natural Science Foundation of China(21829501); National Natural Science Foundation of China(21222301); National Natural Science Foundation of China(21171170); National Natural Science Foundation of China(21528303); Hefei National Laboratory for Physical Sciences at the Microscale(KF2020102); Anhui University(and the provision of ConfotecTM MR520 fluorescence/Raman spectrometer)(S020118002/113); CASHIPS Director’s Fund(BJPY2019A02); Key Program of the 13th five-year plan, CASHIPS(KP-2017-16); Collaborative Innovation Program of Hefei Science Center, CAS(2020HSC-CIP005)

The study of phosphine-protected gold nanocluster can be dated back to 1969, however, the RP-Au-PR motif has not been reported until now. Meanwhile, its analogue RS-Au-SR motif was often reported in thiolated gold nanoclusters, being of multiple functions (e.g., enhancing the luminescence). Herein, we successfully synthesized a monodisperse gold-silver nanocluster: [Au10Ag4(Dppp)5Cl4]Cl2 (Au10Ag4 NC, where the Dppp represents 1,3-diphenylphosphine propane, and NC represents nanocluster) by introducing the reducing agent (NaBH4) in an dichloromethane-ethanol solution of chloroauric acid, silver nitrate and 1,3-diphenylphosphine propane. Hydrochloric acid was added to promote the nanocluster size-focusing. Au10Ag4 NC is unstable in dichloromethane and will be transformed into another nanocluster [Au9Ag4(Dppp)4Cl4]Cl (Au9Ag4 NC). The structures and compositions of Au10Ag4 and Au9Ag4 NCs have been determined by single crystal X-ray crystallography and electrospray ionization mass spectrometry (ESI-MS). Au10Ag4 NC possesses an ico sahedral Au9Ag4 core, which is protected by a special RP-Au-PR motif, diphosphine and halogen ligands; Au9Ag4 NC has an icosahedral Au9Ag4 metal core protected by bisphosphine and halogen ligands, thus the major structural difference between Au10Ag4 and Au9Ag4 NCs is the RP-Au-PR motif. The motif can be self-vanished in Au10Ag4 NC when dichloromethane acts as the solvent, resulting in the formation of Au9Ag4 NC as mentioned above; on the other hand, the motif can self-bear in Au9Ag4 NC when the solvent is ethanol instead of dichloromethane, resulting in the formation of Au10Ag4 NC. The two nanoclusters showed similar ultraviolet-visible-near infrared (UV/Vis/NIR) absorption spectra except for slight shift of the profile, indicating that the RP-Au-PR motif has no essential influence on the electronic structure of nanocluster, which was supported by density functional theory (DFT) calculations. However, the photoluminescence quantum yield of Au10Ag4 NC (10.32%) is 19 times higher than that of Au9Ag4 NC (0.52%), ascribing to the enhancement of charge transfer and structure rigidity induced by the motif. This work provides new views to the structure and photoluminescence of gold-silver nanocluster, has important implications for the structure-property understanding and the property improvement.

Key words: metal nanocluster, RP-Au-PR motif, photoluminescence