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

doi:10.6023/A21110499

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

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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

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)

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

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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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Fig. & Tab. 5

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

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

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)

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

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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