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2022 , Vol. 80 >Issue 1: 1 - 6

DOI: https://doi.org/10.6023/A21110499

研究通讯

单个、自生的RP-Au-PR结构增强金属纳米团簇的光致发光量子产率19倍

  • 许道兰 ,
  • 杨颖 ,
  • 范文涛 ,
  • 何宗兵 ,
  • 邹家丰 ,
  • 冯磊 ,
  • 李漫波 ,
  • 伍志鲲
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  • 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
†These authors contributed equally to this work.
*E-mail: ;
*E-mail: ;

收稿日期: 2021-11-05

  网络出版日期: 2021-11-17

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)

收起

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

  • Daolan Xu ,
  • Ying Yang ,
  • Wentao Fan ,
  • Zongbing He ,
  • Jiafeng Zou ,
  • Lei Feng ,
  • Man-Bo Li ,
  • Zhikun Wu
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  • 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 date: 2021-11-05

  Online published: 2021-11-17

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)

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摘要

膦保护金纳米团簇的研究可追溯到1969年, “RP-Au-PR” (R为烷基)结构在膦保护的金纳米团簇上目前还未见报道, 而相似的 “RS-Au-SR” 结构在硫醇保护金纳米团簇中经常被发现, 其具有多种功能(例如增强团簇发光). 本工作以双膦作为配体成功合成出原子层次单分布的金银纳米团簇[Au10Ag4(Dppp)5Cl4]Cl2 (Au10Ag4 NC, Dppp为1,3-双(二苯基膦)丙烷), 首次发现它具有 “RP-Au-PR” 结构. 有趣的是, 当二氯甲烷作为溶剂时, 该结构可在Au10Ag4 NC中自行消失, 生成[Au9Ag4(Dppp)4Cl4]Cl (Au9Ag4 NC); 另一方面, 当乙醇为溶剂时, 该结构可在Au9Ag4 NC中自行生成, 从而转变成Au10Ag4 NC. 两个团簇的紫外-可见-近红外(UV/Vis/NIR)吸收峰除了有轻微的位移外, 没有显著的区别, 暗示着 “RP-Au-PR” 结构对团簇的电子结构没有根本影响, 这一点也被密度泛函理论(DFT)计算所支撑. 该结构促使Au10Ag4 NC的光致发光量子产率比Au9Ag4 NC的提高了19倍(达到10.32%), 这归因于 “RP-Au-PR” 结构诱导的电荷转移和刚性的增强. 本工作揭示了新的团簇结构和发光现象, 对团簇构效关系的理解和性能改善有重要的启发.

关键词： 金属纳米团簇; “RP-Au-PR”结构; 光致发光

本文引用格式

许道兰 , 杨颖 , 范文涛 , 何宗兵 , 邹家丰 , 冯磊 , 李漫波 , 伍志鲲 . 单个、自生的RP-Au-PR结构增强金属纳米团簇的光致发光量子产率19倍[J]. 化学学报, 2022 , 80(1) : 1 -6 . DOI: 10.6023/A21110499

Abstract

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

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