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

doi:10.6023/A21110499

化学学报 ›› 2022, Vol. 80 ›› Issue (1): 1-6.DOI: 10.6023/A21110499 上一篇下一篇

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^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^,^*()

^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 Xu^a^,^b, Ying Yang^a^,^b, Wentao Fan^b^,^c^,^a, Zongbing He^a^,^b, Jiafeng Zou^a^,^b, Lei Feng^a^,^b, Man-Bo Li^a^,^b(), Zhikun Wu^a^,^b()

^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)

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摘要/Abstract

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Au₉Ag₄NC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

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 (Au₁₀Ag₄NC, 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 (Au₉Ag₄NC). 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 Au₉Ag₄core, which is protected by a special RP-Au-PR motif, diphosphine and halogen ligands; Au₉Ag₄NC has an icosahedral Au₉Ag₄metal core protected by bisphosphine and halogen ligands, thus the major structural difference between Au₁₀Ag₄ and Au₉Ag₄NCs 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 Au₉Ag₄NC as mentioned above; on the other hand, the motif can self-bear in Au₉Ag₄NC when the solvent is ethanol instead of dichloromethane, resulting in the formation of Au₁₀Ag₄NC_.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 Au₉Ag₄NC (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

引用此文

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.

Daolan Xu, Ying Yang, Wentao Fan, Zongbing He, Jiafeng Zou, Lei Feng, Man-Bo Li, Zhikun Wu. Single, Self-Born RP-Au-PR Motif Boosts 19-Fold Photoluminescence Quantum Yield of Metal Nanocluster[J]. Acta Chimica Sinica, 2022, 80(1): 1-6.

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图/表 5

图1. Au9Ag4 NC (a)和Au10Ag4 NC (b)的电喷雾电离质谱, 插图: 实验(黑色)和模拟(红色)同位素分布的对比

Figure 1. ESI-MS of Au9Ag4 NC (a) and Au10Ag4 NC (b), inset: the comparison of the experimental (black) and simulated (red) isotope patterns

图2. Au9Ag4 NC和Au10Ag4 NC的结构示意图. 颜色代码: 橙色、深绿色, Au; 红色, Ag; 紫色, P; 亮绿色, Cl; 浅灰色, C. 为了清晰起见, 省略了所有的苯环和H原子

Figure 2. Schematic illustration of Au9Ag4 NC and Au10Ag4 NC structures. Color legend: orange, dark green, Au; red, Ag; purple, P; bright green, Cl; gray, C. All benzene rings and H atoms are omitted for clarity

图3. 计算的Au9Ag4 NC (a) 和Au10Ag4 NC (b) 的UV/Vis/NIR吸收光谱. Au9Ag4 NC (c) 和Au10Ag4 NC (d) 的Kohn-Sham轨道

Figure 3. Calculated UV/Vis/NIR absorption spectra of Au9Ag4 NC (a) and Au10Ag4 NC (b). Kohn-Sham orbitals of Au9Ag4 NC (c) and Au10Ag4 NC (d)

图4. Au9Ag4 NC和Au10Ag4 NC在乙腈中的PL激发光谱(λEM=750 nm) (a)和发射光谱(λEX=405 nm) (b). Au9Ag4 NC (c)和Au10Ag4 NC (d)在乙腈中的PL寿命衰减图

Figure 4. PL excitation (λEM=750 nm) (a) and emission spectra (λEX=405 nm) (b) of Au9Ag4 NC and Au10Ag4 NC in acetonitrile. PL lifetime decay diagrams of Au9Ag4 NC (c) and Au10Ag4 NC (d) in acetonitrile

图5. (a) 通过UV/Vis/NIR吸收光谱和制备型薄层色谱(PTLC)监测25 ℃下在二氯甲烷中Au10Ag4 NC向Au9Ag4 NC的转变. (b) 通过UV/Vis/NIR吸收光谱和PTLC监测60 ℃下在乙醇中Au9Ag4 NC向Au10Ag4 NC的转变

Figure 5. (a) Conversion of Au10Ag4 NC to Au9Ag4 NC at 25 ℃ in dichloromethane monitored by UV/Vis/NIR absorption spectra and preparative thin layer chromatography (PTLC). (b) Conversion of Au9Ag4 NC to Au10Ag4 NC at 60 ℃ in ethanol monitored by UV/Vis/NIR absorption spectra and PTLC

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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

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

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