Module Replacement of Gold Nanoparticles by a Pseudo-AGR Process

Citation: Jin Fengming, Dong Hongwei, Zhao Yan, Zhuang Shengli, Liao Lingwen, Yan Nan, Gu Wanmiao, Zha Jun, Yuan Jinyun, Li Jin, Deng Haiteng, Gan Zibao, Yang Jinlong, Wu Zhikun. Module Replacement of Gold Nanoparticles by a Pseudo-AGR Process[J]. Acta Chimica Sinica, 2020, 78(5): 407-411. doi: 10.6023/A20040134 shu

通过赝反伽伐尼反应实现金纳米粒子模块替换

a.
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合肥 230031
b.
中国科学技术大学合肥 230026
c.
安徽大学物质科学与信息技术研究院合肥 230601
d.
中国科学技术大学合肥微尺度物质科学国家研究中心合肥 230026
e.
清华大学生命科学学院清华大学-北京大学生命科学联合中心北京 100084
f.
清华大学生命科学学院生物信息学教育部重点实验室北京 100084

通讯作者: 甘自保, zbgan@iim.ac.cn
伍志鲲, zkwu@issp.ac.cn

基金项目:
国家自然科学基金 21603234

国家自然科学基金 21222301

中国博士后科学基金会 Y94G4E356B

国家自然科学基金 21971246

中国科学院/国家外国专家局创新团队国际合作伙伴计划和合肥物质科学技术中心方向项目培育基金 2017FXCX002

中国科学院合肥研究院院长基金 BJPY2019A02

国家自然科学基金 21905284

项目受国家自然科学基金(Nos.21925303, 21971246, 21829501, 21905284, 21771186, 21603234, 21222301, 21171170, 21528303)、中国博士后科学基金会(Y94G4E356B)、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/国家外国专家局创新团队国际合作伙伴计划和合肥物质科学技术中心方向项目培育基金(2017FXCX002)资助

国家自然科学基金 21171170

国家自然科学基金 21771186

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

国家自然科学基金 21925303

国家自然科学基金 21829501

国家自然科学基金 21528303

摘要: 通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现，涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体，但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程，却增强了它的发射，赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化，对于研究这两种效应之间的相互影响也具有重要的启示.

关键词:

English

Module Replacement of Gold Nanoparticles by a Pseudo-AGR Process

a.
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China
b.
University of Science and Technology of China, Hefei 230026, China
c.
Institute of Physical Science and Information Technology, Anhui University, Hefei 230601, China
d.
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
e.
Tsinghua University-Peking University Joint Center for Life Sciences, School of Life Sciences, Tsinghua University, Beijing 100084, China
f.
MOE Key Laboratory of Bioinformatics, School of Life Sciences, Tsinghua University, Beijing 100084, China
† These authors contributed equally to this work.

Corresponding author: Gan Zibao, zbgan@iim.ac.cn Wu Zhikun, zkwu@issp.ac.cn

Received Date: 30 April 2020
Available Online: 15 May 2020
Fund Project:

Project supported by the National Natural Science Foundation of China (Nos. 21925303, 21971246, 21829501, 21905284, 21771186, 21603234, 21222301, 21171170, 21528303), China Postdoctoral Science Foundation (Y94G4E356B), CASHIPS Director's Fund (BJPY2019A02), Key Program of 13th five-year plan, CASHIPS (KP-2017-16), CAS/SAFEA International Partnership Program for Creative Research Teams and Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXCX002)

Abstract: Precisely modulating the structure of nanoparticles in a controlled manner is still a challenging and inspiring topic. Although the single or few-metal atom tailoring of gold nanoparticles has been reported, local structural replacement involving over three net metal atoms (module replacement, MR) has not been hitherto achieved. Herein, we report the synthesis of cyclohexanethiolated metal nanoclusters (NCs) Au₄₈(CHT)₂₆ and their MR by a so-called pseudo-anti-galvanic reaction (AGR) process. The MR product Au₃₇(CHT)₂₃ shares a similar Au₃₁(CHT)₁₂ unit with its predecessor Au₄₈(CHT)₂₆; however, it differs from its predecessor in the remaining section (Au₆(CHT)₁₁ vs. Au₁₆(CHT)₁₄), as revealed by single-crystal X-ray crystallography (SCXC). Interestingly, the MR inhibits the photothermy but enhances the emission of Au₄₈(CHT)₂₆ NCs, which might endow the as-obtained NC better potential for bi(multiple)-functional application. The counter effects of the MR on the emission and photothermy indicate that photoluminescence and photothermy can be at least partly converted into each other, which has some important implications for the understanding of their interaction.

Key words:

1.   Introduction

For organic molecules, people can precisely tailor the specific substructure without altering the major carbon bones to endow them with various functions. Meanwhile, for traditional nanoparticles, it is nearly impossible to precisely tune the structure at the atomic level. With the development of wet chemistry, breakthroughs have been achieved in the synthesis of ultrasmall metal nanoparticles (often called nanoclusters (NCs)) in the past decades.^[1-10] Metal NCs have the merits of mono-dispersity, ^[11-14] well-defined compositions and structures, ^{[1, 15-22]} intriguing physicochemical properties^{[7, 23-28]} and so on. In particular, these ultrasmall nanoparticles provide opportunities for precisely tuning the overall or even partial structure (including specific sites), which is of great significance to understand the structure-property correlation and improve the performance in a sustainable way. The overall structure transformation has been repeatedly reported; for example, Au₂₅ NCs can be converted into Au₂₀, ^[29] Au₂₃, ^[30] Au₂₄, ^[31] Au₂₈, ^[32] or Au₃₈^{[33, 34]} by various methods such as ligand exchange/etching, reduction and acid-induction. Recently, the single or few metal-atom tailoring of metal nanoparticles with the remnant structure untouched has also been accomplished. For example, Jin et al. reported an interesting molecular "surgery"^{[35, 36]} by employing the combined anti-galvanic^[37-39] and pseudo-anti-galvanic reactions.^[31] Wu et al. successfully realized single or few metal-atom addition and replacement by employing an anti-galvanic reaction (AGR)^[40-44] (notably, the same group also introduced the surface single-atom tailoring method recently).^[45] However, to date, the local structural replacement involving over three net metal atoms (Scheme 1) has not been fulfilled no matter the replacement is an elementary reaction or not. For clarification, such a structure manipulation was named module replacement (MR). To explore such a concept, we conducted this study.

Scheme 1

Scheme 1. The illustration of the module replacement process.

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Unlike the common ligands such as 4-tert-butylbenzenethiolate (TBBT), 2, 4-dimethylbenzenethiolate (CHT) (2, 4-DMBT), and p-methylbenzenethiolate (p-MBT), cyclohexanethiolate is short and flexible, making it suitable for this study as a protecting ligand of metal NCs. Actually, cyclohexanethiolated gold NCs have gained extensive interest recently, and several cyclohexanethiolated gold NCs including Au₁₈(CHT)₁₄, ^[46] [Au₂₃(CHT)₁₆]⁻, ^[47] Au₂₈(CHT)₂₀, ^[48] Au₃₄(CHT)₂₂, ^[49] Au₄₂(CHT)₂₆, ^[49] and Au₄₃(CHT)₂₅^[50] have been reported and structurally resolved until now. However, it remains unknown whether the cyclohexanethiolated gold NCs larger than Au₄₃(CHT)₂₅^[50] can be structurally resolved. To address this issue as well, we investigated the synthesis of cyclohexanethiolated gold NCs and obtained a slightly larger NC Au₄₈(CHT)₂₆.

2.   Results and discussion

2.1   ESI-MS

Electrospray ionization mass spectrometry (ESI-MS) was applied to determine the exact molecular formulas of the as-obtained gold NCs. To assist in the ionization, cesium acetate (CsOAC) was added to the NC solution to form positively charged adducts. Notably, the NCs are charge neutral since the charge number is equal to the number of adducted Cs ions, which is further supported by the fact that there were no sound signals in the mass spectra acquired in both the positive and negative ionization modes without the addition of the assistant reagent. As shown in Figure 1a, one dominant peak centered at m/z 6358.95 was shown in the mass spectrum, which can be readily assigned to [Au₄₈(CHT)₂₆Cs₂]²⁺ species (calculated: 6358.37 Da, deviation: 0.58 Da). Therefore, the NC formula was determined to be Au₄₈(CHT)₂₆.

Figure 1

Figure 1. ESI-MS spectra of Au₄₈(CHT)₂₆ (a) and Au₃₇(CHT)₂₃ (b) NCs.

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2.2   SCXC

Single-crystal X-ray crystallography (SCXC) confirms the composition and reveals that the NCs crystallize in the axisymmetric space group P2₁/c with the unit cell comprised of a pair of enantiomers (Figure S1). As shown in Figure 2, the overall structure of Au₄₈(CHT)₂₆ is distinctly different from the previously reported Au₄₈(TBBT)₂₈ NC, which is protected by 28 4-tert-butylbenzenethiolates with a Au₃₁ kernel consisting of face-fused bi-icosahedral Au₂₃ and a special Au₈ bottom cap.^[51] Meanwhile, the structure of Au₄₈(CHT)₂₆ contains a Au₃₅ kernel (Figure 2c) composed of one quasi-fcc Au₂₁ unit (Figure 2a) and one non-fcc Au₁₄ unit (Figure 2b). This quasi-dualpacked-kerneled structure resembles that of Au₄₉(2, 4-DMBT)₂₇, which contains a Au₃₄ kernel consisting of one quasi-fcc Au₂₁ unit and one non-fcc Au₁₃ unit, ^[52] and it has not been previously reported in cyclohexanethiolated metal NCs. The Au₃₅ kernel of Au₄₈(CHT)₂₆ is capped by an exterior shell including four Au₂(SR)₃ dimers, five Au(SR)₂ monomers and four bridging SR thiolates (Figure 2d-2f).

Figure 2

Figure 2. Anatomy of the structure of the Au₄₈(CHT)₂₆ NC: (a) Au₂₁ quasi-fcc unit; (b) Au₁₄ non-fcc unit; (c) Au₃₅ kernel; (d) Au₄₃(CHT)₁₂ framework; (e) Au₄₈(CHT)₂₂ framework; and (f) total structure of Au₄₈(CHT)₂₆. For clarity, C and H are omitted. Color labels: yellow＝S; others＝Au.

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A pseudo-anti-galvanic reaction (AGR) was employed for the MR of the as-obtained Au₄₈(CHT)₂₆ due to that pseudo-AGR has shown great potential to modulate the structure of gold NCs in a controlled way.^{[31, 35, 44]} Luckily, we successfully achieved the MR manipulation and obtained a novel NC, whose composition was determined to be Au₃₇(CHT)₂₃ (Figure 1b). SCXC further confirms this composition and reveals that Au₃₇(CHT)₂₃ crystallizes in the axisymmetric space group P-1, with the unit cell comprised of a pair of enantiomers (Figure S2). The overall structure of Au₃₇(CHT)₂₃ is composed of an Au₂₅ kernel capped by an outer shell containing one Au₃(SR)₄ trimer, three Au₂(SR)₃ dimers, three Au(SR)₂ monomers and four bridging SR thiolates (Figure S3). It can be readily found that the Au₃₅ kernel of Au₄₈(CHT)₂₆ can be regarded as the net addition of one Au₁₀ unit to the Au₂₅ kernel of Au₃₇(CHT)₂₃ (Figure 3a-3f). In the Au₁₀ unit, four Au atoms belong to the part of the quasi-fcc structure, and the other six Au atoms belong to the part of the non-fcc structure. Of note is that the proportion of fcc structure in the kernel of Au₃₇(CHT)₂₃ increases compared to that in the kernel of Au₄₈(CHT)₂₆. However, the Au₂₅ kernel connected staples in Au₃₇(CHT)₂₃ are the same as those in Au₄₈(CHT)₂₆, i.e., Au₃₇(CHT)₂₃ and Au₄₈(CHT)₂₆ share the same Au₃₁(CHT)₁₂ section with the other section different (Au₆(CHT)₁₁ vs. Au₁₇(CHT)₁₄). Therefore, the transformation from Au₄₈(CHT)₂₆ to Au₃₇(CHT)₂₃ can be regarded as a MR process (Figure 4), and the net reaction can be described in Table 1. DFT calculations (see Supporting Information for the details) reveal the formation energy (ΔE) is －22.0 eV, indicating that the reaction is energy-favorable. It should be noted that Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ can also be regarded as kernel homologues previously proposed by Zhuang et al.^[51] The local internal structural change also leads to the remarkable alternation of the external structure (crystallographic arrangement). As shown in Figure S4, the Au₄₈(CHT)₂₆ adopts the "ABCD" arrangement, which is essentially different from the "ABAB" arrangement in Au₃₇(CHT)₂₃ crystals.

Figure 3

Figure 3. Anatomy of structures of Au₃₇(CHT)₂₃ and Au₄₈(CHT)₂₆ NCs: (a) Au₂₁ quasi-fcc unit of Au₄₈(CHT)₂₆; (b) Au₁₇ quasi-fcc unit of Au₃₇(CHT)₂₃; (c) Au₁₄ non-fcc unit of Au₄₈(CHT)₂₆; (d) Au₈ non-fcc unit of Au₃₇(CHT)₂₃; (e) Au₃₅ kernel of Au₄₈(CHT)₂₆; (f) Au₂₅ kernel of Au₃₇(CHT)₂₃; (g) total staple motifs of Au₄₈(CHT)₂₆; (h) total staple motifs of Au₃₇(CHT)₂₃; (i) total structure of Au₄₈(CHT)₂₆; and (j) total structure of Au₃₇(CHT)₂₃. For clarity, C and H are omitted. Color labels: yellow, orange and pink＝S; others＝Au.

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Figure 4

Figure 4. The illustration of module replacement process from Au₄₈(CHT)₂₆ to Au₃₇(CHT)₂₃.

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Table 1

Table 1. The net reaction and the formation energy estimation

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2.3   Photothermy and photoluminescence

More interest pertains to the property tuning of the MR. Photoluminescence is an intriguing property that has been extensively studied, ^[53-61] while photothermy is rarely studied for well-defined NCs despite its potential in a large range of fields such as energy conversion^{[62, 63]} and biomedicine.^[64-68] To the best of our knowledge, the combination study of photoluminescence and photothermy for well-defined metal NCs has not yet been examined. Herein, we investigated and compared their photoluminescence and photothermy. As shown in Figure 5 and Figures S5 and S6, both NCs exhibit obvious photothermal effects. Specifically, the temperatures of Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ solutions with a concentration of 0.1 mmol/L increased by 17.2 ℃ and 12.0 ℃ under the investigated conditions with photothermal conversion efficiencies of 42.9% and 30.3%, respectively (see Figure 5a and Supporting Information), indicating that Au₄₈(CHT)₂₆ had a stronger photothermal effect than Au₃₇(CHT)₂₃, which is also supported by their infrared thermal imaging results (Figure S5). However, the emission intensity of Au₃₇(CHT)₂₃ is about three-fold the intensity of Au₄₈(CHT)₂₆ (Figure 5b), indicating that emission and photothermy are in a balance^[69-71] and they can be at least partly converted into each other, which was not previously reported for well-defined NCs. These facts also indicate that MR can efficiently tune the properties of metal NCs. It should be noted that such bi(multiple)-functional NCs are particularly promising for practical applications. For example, such materials might be applied for both imaging and curing cancer since they have both NIR photoluminescence and photothermy properties. Nevertheless, this is beyond the scope of the current study and should be pursued in the future.

Figure 5

Figure 5. (a) The photothermal effects of Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ with a concentration of 0.1 mmol/L under 0.25 W/cm² 650 nm laser irradiation (laser beam size: 1 cm²). (b) The photoluminescence spectra of Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ (the excitation wavelength λ_ex＝650 nm).

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3.   Conclusion

In summary, we have succeeded in synthesizing the largest cyclohexanethiolated metal NCs structurally resolved by ESI-MS and SCXC, revealing that one NC is composed of 48 gold atoms and 26 cyclohexanethiolates with a quasi-dual-packed-kerneled structure not reported in cyclohexanethiolated metal NCs. For the first time, we fulfill the MR manipulation of metal NCs by a pseudo-AGR process and obtain another novel NC Au₃₇(CHT)₂₃, which can also be regarded as the kernel homologue of Au₄₈(CHT)₂₆. DFT calculations also support the transformation from Au₄₈(CHT)₂₆ to Au₃₇(CHT)₂₃ is energy-favorable. The MR weakens the photoluminescence but strengthens the photothermy in this work, indicating that photoluminescence and photothermy are in a balance and they can be at least partly converted into each other for NCs. The property tuning by MR might endow NCs better potential for bi(multiple)-functional applications, which need to be pursued in the future. Overall, our work not only provides novel insights into the structures of metal NCs but also has important implications for future tuning of the compositions, structures and properties of metal nanoparticles and understanding of the interactions between various properties as well.

4.   Experiment

The synthesis is facile. Briefly, the precursors of the polydisperse Au_x(CHT)_y clusters were first synthesized by reducing the Au(I)-(CHT) complexes with NaBH₄. Then, the Au_x(CHT)_y was treated with excess cyclohexanethiol at 80 ℃ for 15 h. The crude products were washed with excess methanol and then purified by preparative thin-layer chromatography (PTLC) (see Supporting Information for the experimental details). The as-purified NCs were recrystallized from the solution of toluene/methanol (V:V＝4:3) at 0 ℃ over one week.

Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn
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Scheme 1 The illustration of the module replacement process.

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Figure 1 ESI-MS spectra of Au₄₈(CHT)₂₆ (a) and Au₃₇(CHT)₂₃ (b) NCs.

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Figure 2 Anatomy of the structure of the Au₄₈(CHT)₂₆ NC: (a) Au₂₁ quasi-fcc unit; (b) Au₁₄ non-fcc unit; (c) Au₃₅ kernel; (d) Au₄₃(CHT)₁₂ framework; (e) Au₄₈(CHT)₂₂ framework; and (f) total structure of Au₄₈(CHT)₂₆. For clarity, C and H are omitted. Color labels: yellow＝S; others＝Au.

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Figure 3 Anatomy of structures of Au₃₇(CHT)₂₃ and Au₄₈(CHT)₂₆ NCs: (a) Au₂₁ quasi-fcc unit of Au₄₈(CHT)₂₆; (b) Au₁₇ quasi-fcc unit of Au₃₇(CHT)₂₃; (c) Au₁₄ non-fcc unit of Au₄₈(CHT)₂₆; (d) Au₈ non-fcc unit of Au₃₇(CHT)₂₃; (e) Au₃₅ kernel of Au₄₈(CHT)₂₆; (f) Au₂₅ kernel of Au₃₇(CHT)₂₃; (g) total staple motifs of Au₄₈(CHT)₂₆; (h) total staple motifs of Au₃₇(CHT)₂₃; (i) total structure of Au₄₈(CHT)₂₆; and (j) total structure of Au₃₇(CHT)₂₃. For clarity, C and H are omitted. Color labels: yellow, orange and pink＝S; others＝Au.

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Figure 4 The illustration of module replacement process from Au₄₈(CHT)₂₆ to Au₃₇(CHT)₂₃.

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Figure 5 (a) The photothermal effects of Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ with a concentration of 0.1 mmol/L under 0.25 W/cm² 650 nm laser irradiation (laser beam size: 1 cm²). (b) The photoluminescence spectra of Au₄₈(CHT)₂₆ and Au₃₇(CHT)₂₃ (the excitation wavelength λ_ex＝650 nm).

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Table 1. The net reaction and the formation energy estimation

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