Oxidation-Induced Transformation of Eight-Electron Gold Nanoclusters

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Oxidation-Induced Transformation of 8-electron Gold Nanoclusters: [Au23(SR)16]- to [Au28(SR)20]0 Tatsuya Higaki, Chong Liu, Yuxiang Chen, Shuo Zhao, Chenjie Zeng, Renxi Jin, Shuxin Wang, Nathaniel L Rosi, and Rongchao Jin J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.6b03061 • Publication Date (Web): 01 Feb 2017 Downloaded from http://pubs.acs.org on February 3, 2017

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The Journal of Physical Chemistry Letters

Oxidation-Induced Transformation of 8-electron Gold Nanoclusters: [Au23(SR)16]− to [Au28(SR)20]0 Tatsuya Higaki,† Chong Liu,‡ Yuxiang Chen,† Shuo Zhao,† Chenjie Zeng,† Renxi Jin,†,§ Shuxin Wang,†, Nathaniel L. Rosi,‡ Rongchao Jin*,† †

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United

States. ‡Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15213, United States. §School of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China. Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University, Hefei, Anhui 230601, China. AUTHOR INFORMATION Corresponding Author [email protected]

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ABSTRACT. Here we report an oxidation-induced transformation of [Au23(S-c-C6H11)16]−TOA+ (S-c-C6H11:

cyclohexanethiolate,

TOA:

tetraoctylammonium)

to

[Au28(S-c-C6H11)20]0

nanocluster by H2O2 treatment under ambient conditions. This is the first example of oxidationinduced transformation of one stable size to another with atomic precision. The product was crystallized and analyzed by X-ray crystallography. Further insights into the transformation process were obtained by monitoring the process with optical spectroscopy and also by electrochemical analysis. This work adds a new dimension to the recently established transformation chemistry of nanoclusters that involves size and structure transformations.

TOC GRAPHIC


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Atomically precise gold nanoclusters with molecular purity have recently been studied intensively along with the development of new synthetic methods and the characterization of atomic structures by single crystal X-ray diffraction analysis.1-10 With respect to the properties, the redox behavior of nanoclusters has gained wide interest because different charge states of the nanocluster affect the functionalities, such as the geometrical structure,11-19 magnetism,14,20-22 catalytic reactivity,23-26 photoluminescence,27-29 and electron dynamics.30 For example, [Au25(PET)18]− (PET = SCH2CH2Ph, 2-phenylethanethiolate) is diamagnetic but becomes paramagnetic when the nanocluster is oxidized to [Au25(PET)18]0 by atmospheric oxygen.13,14 Interestingly, the Au25(PET)18 nanocluster can also have a positively charged state31,32 which has a somewhat different conformation15 compared to the anionic and neutral nanoclusters.11-13 Recently, the critical roles of ligands on the nanocluster structure33-36 and properties (e.g., catalytic activity)37,38 have been revealed, which has also largely expanded the size library of nanoclusters,1 but the number of robust Aun(SR)m nanoclusters with multiple charge states is still limited except the case of [Au25(SR)18]q. The exceptional behavior of [Au25(SR)18]q was also observed in reactivity toward metal ions,39-41 halides42 and other nanoclusters,43 leading to the formation of different-size atomically precise nanoclusters. The rich chemistry of [Au25(SR)18]q motivated us to investigate the redox property (in particular the oxidation) of [Au23(SR)16]−,44 as it is another unique nanocluster bearing a -1 charge and possessing 8 nominal free valence electrons as the case of [Au25(SR)18]−.14,45 Such an investigation will allow one to further understand the relationship between the stability and the redox property, and broadly the transformation chemistry of nanoclusters. Here we report an oxidation-induced transformation of [Au23(S-c-C6)16]− (counter ion: TOA+) to [Au28(S-c-C6)20]0 nanocluster (where c-C6 stands for C6H11, the same hereafter) by H2O2 treatment without introducing any other reagents such as new ligands (Figure 1). Furthermore, the product was crystallized and X-ray crystallography analysis revealed that the oxidized nanocluster possess the same atomic structure as the recently reported [Au28(S-c-C6)20]0 nanocluster which was synthesized by ligand-exchange of Au28(TBBT)20 (TBBT=S-Ph-C(CH3)3, 4-tert-benenzenethiolate) with c-C6-SH.37 Although the ligand-exchange-induced size/structure transformation (LEIST) of gold nanoclusters46 has been established for accessing different sizes of nanoclusters, this is the first example of oxidation-induced size/structure transformation (OIST), in which one stable size of gold nanocluster can be transformed into another by simple 3 Environment ACS Paragon Plus


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oxidation. It thus adds a new dimension to the transformation methodology and reveals the rich chemistry of nanoclusters.

Figure 1. Oxidization-induced transformation [Au23(S-c-C6)16]− to [Au28(S-c-C6)20]0 nanocluster. The Au23 structure is redrawn from ref. 44.

The transformation proceeds to completion within 2 hrs under simple reaction conditions. First, the [Au23(S-c-C6)16]− nanocluster was prepared by a literature procedure.44 The Au23 nanocluster was dissolved in dichloromethane, and mixed with an aqueous solution of H2O2. Then, the biphasic solution was stirred for 2 hrs. The color of the organic phase gradually changed from purple to dark red. After the completion of oxidation reaction, the organic salts were washed out by repetitive precipitation using methanol and acetonitrile. Unlike the ligandexchange reaction with excess thiol,46 both Au atoms and ligand molecules in the [Au28(S-cC6)20]0 product are exclusively from the starting [Au23(S-c-C6)16]− nanocluster. In this reaction, the molar ratio of ligand (i.e., 16/20 = 0.80) is slightly smaller than that of Au atoms (i.e., 23/28 = 0.82). Therefore, the number of ligand is the limiting factor for the maximum yield of cluster product (80 %), and the experimental yield (>70 %) is sufficiently high in terms of the recovery of cyclohexanethiolate. Single crystals of the product were obtained by vapor diffusion of methanol into a toluene solution of the [Au28(S-c-C6)20]0 nanocluster. The single crystal X-ray diffraction analysis (Table S1, 2) revealed that the [Au28(S-c-C6)20]0 nanocluster obtained by this method has an Au20 kernel with face-centered cubic (fcc) arrangement protected by two monomeric staple motifs (i.e., Au(SR)2) and two trimeric staple motifs (i.e., Au3(SR)4) as well as 8 plain bridging thiolates


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(Figure 1, right). This structure is the same as the recently reported [Au28(S-c-C6)20]0 nanocluster which was synthesized via ligand exchange reaction using Au28(TBBT)20 as a starting material,37 despite the distinct differences in the reaction conditions such as the temperature (room temperatures vs. 80 ºC) and reactants (H2O2 vs. excess c-C6-SH). Considering the fact that the [Au28(S-c-C6)20]0 nanocluster obtained by different methods have the same structure (Table S3), the size/structure of the nanocluster is thermodynamically determined and thus of high stability. The oxidation process was monitored with temporal measurements of UV-Vis absorption spectra (Figure 2). Before the H2O2 treatment, the absorption spectrum of [Au23(S-c-C6)16]− showed a prominent peak at 570 nm and a shoulder around 450 nm, as reported previously.44 After the addition of H2O2 solution, the intensity of the 570-nm peak started to decrease within 10 min. By monitoring the absorbance at 570 nm at time intervals of 5 min, we found that the spectral change was nearly completed after 1 hr (Figure 2). In this series of spectra, four isosbestic points were found at 355, 468, 526 and 641 nm (indicated by arrows in Figure 2). This observation indicates that there are only two species involved in this transformation and it can serve as the evidence for direct transformation of the [Au23(S-c-C6)16]− to [Au28(S-c-C6)20]0 nanocluster without any metastable intermediates. Also, the optical spectrum of the final product shows absorption peaks at 435 and 549 nm, which match with peak positions of the previously reported [Au28(S-c-C6)20]0 nanocluster (with peaks at 355, 460 and 550 nm).37

Figure 2. Time evolution of UV-Vis spectra of [Au23(S-c-C6)16]− nanocluster with H2O2 treatment. Black arrows indicate the position of isosbestic points.



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In order to further examine the reaction product, electrospray-ionization (ESI) mass spectrometry was performed using cesium acetate (CsOAc) as a charging reagent to the nanocluster via forming cesium adducts. The positive ion mode mass spectrum (Figure 3) shows that the major product of the reaction was the Au28 nanocluster based on the peak assignment of the most intense peak as the [Au28(S-c-C6)20]Cs+ adduct. The experimentally obtained peak matches well with the simulated isotope distribution pattern (Figure 3 inset), thus, confirming the peak assignment.

Figure 3. ESI mass spectrum of the reaction product (i.e. the [Au28(SR)20]0 nanocluster). The asterisk indicates a fragment species with one ligand lost (i.e., -SR).

To obtain further insight into the reaction mechanism, differential pulse voltammetry (DPV) were performed for both [Au23(S-c-C6)16]− and [Au28(S-c-C6)20]0 nanoclusters (Figure 4). In the DPV of [Au23(S-c-C6)16]−, the electrochemical HOMO-LUMO gap was found to be 1.85 eV after subtraction of the charging energy. This value is consistent with the optical gap (1.88 eV) observed from the UV-Vis spectrum of [Au23(S-c-C6)16]− by extrapolation to zero absorbance. The DPV of [Au28(S-c-C6)20]0 nanocluster showed an electrochemical HOMOLUMO gap (1.77 eV), which is consistent with the optical gap observed from the UV-Vis spectrum (~1.7 eV). Also, the DPV of [Au23(S-c-C6)16]− has no overlaps of peak positions with those of [Au28(S-c-C6)20]0 (see Table S4 for peak values), so all the redox peaks in the DPV of [Au23(S-c-C6)16]− have no interference from the [Au28(S-c-C6)20]0 nanocluster formed in situ on


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the electrode surface during the DPV measurement although [Au28(S-c-C6)20]0 was found to form with applying certain potential to [Au23(S-c-C6)16]− continuously (vide infra).

Figure 4. DPV of [Au23(S-c-C6)16]− (top) and [Au28(S-c-C6)20]0 (bottom) nanoclusters. The peak indicated with an asterisk comes from residual O2 after N2 bubbling.

It is worth noting that the negatively charged [Au25(PET)18]− nanocluster can be gradually oxidized by atmospheric O2 or H2O2,13,14 as well as electrochemically,20 but in those cases there was no occurrence of transformation to other sizes, instead, the nanocluster retained its core and staple structure, leading to neutral [Au25(PET)18]0 nanocluster,13 and controlled oxidation further led to the [Au25(PET)18]+ nanocluster,31,32 with the structure still maintained,15 but over-oxidation was found to result in decomposition of [Au25(PET)18]−. In order to prove that the H2O2 treatment process of [Au23(S-c-C6)16]− does not involve the multiple step over-oxidation with metastable intermediates such as neutral Au23 nanocluster, bulk electrolysis was performed for



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controlled oxidation based on the first oxidation peak in the DPV. In a dichloromethane solution of the Au23 nanocluster, a voltage of 0.3 V (vs. Ag/AgCl) was applied for 5 hrs in the presence of TBAPF6 (tetrabutylammonium hexafluorophosphate) as electrolyte. The UV-Vis spectrum of the electrolysis product is found to be the same as that of the product made by oxidation with H2O2 (Figure S1), thus the result indicates that the H2O2 treatment process involves a direct transformation from [Au23(S-c-C6)16]− to [Au28(S-c-C6)20]0 without over-oxidation of metastable intermediates such as neutral Au23 nanocluster. The treatment of [Au23(S-c-C6)16]− with other oxidants such as O2 13 or Ce(SO4)2 47,48 resulted in the formation of the same product evidenced by their similar UV-Vis spectra (Figure S1), further confirming that the reaction is oxidationinduced transformation. Interestingly, both [Au23(S-c-C6)16]− and [Au28(S-c-C6)20]0 nanoclusters were found to have the same three types of surface motifs, and the same fcc packing mode in the core (Figure 5). Specifically, both nanoclusters possess two monomeric staples, with one staple being located at the top of the cluster and the other at the bottom in a similar manner for both clusters (Figure 5A, B). Also, both nanoclusters possess two trimeric staples; the latter are arranged parallelly in [Au23(S-c-C6)16]− but nearly perpendicularly in [Au28(S-c-C6)20]0 (Figure 5A, D). Both nanoclusters also possess plain bridging thiolates (4 vs. 8) for surface protection. As for the core structure, the Au15 core of [Au23(S-c-C6)16]− consists of 13 gold atoms in fcc-based cuboctahedral arrangement and 2 face-capping gold atoms in opposite sites.44 The [Au28(S-c-C6)20]0 nanocluster possesses an interpenetrated bicuboctahedral Au20 core, so it also has a fcc-based core structure. It is of interest to note that both the starting nanocluster and the product possess the same fcctype of kernels. The role of the fcc kernel in the transformation process remains to be elucidated in future work.


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Figure 5. Staple motifs and kernel structures of [Au23(S-c-C6)16]− (A, C) and [Au28(S-c-C6)20]0 (B, D). Color labels: magenta = Au in the kernel, green = Au in the monomeric staple motif, blue = Au in the dimeric staple motif, yellow = S). Carbon tails are omitted for clarity. The Au23 structure is redrawn from ref. 44.

In summary, we have revealed a transformation of [Au23(S-c-C6)16]− to [Au28(S-c-C6)20]0 nanocluster induced by H2O2 treatment under ambient conditions. This oxidation-induced reaction proceeds with high yield (>70%) and the crystallographic structure of the [Au28(S-cC6)20]0 product is determined. Although the size and atomic structure are transformed during the conversion of [Au23(S-c-C6)16]− to [Au28(S-c-C6)20]0, their core and surface motif types as well as the nominal electron count (8e) are all retained. Insights into the mechanism are obtained by UVVis spectroscopic and electrochemical analyses. This work demonstrates the potential of oxidation-induced size/structure transformation (OIST), in contrast with the ligand-exchangeinduced size/structure transformation (LEIST), for future accessing to new Au nanoclusters which cannot be made by ligand-exchange and thermal etching.

ASSOCIATED CONTENT AUTHOR INFORMATION Corresponding Author



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*[email protected]

Notes The authors declare no competing financial interests. ACKNOWLEDGMENT The work is supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-15-1-9999 (FA9550-15-1-0154) and the Camille Dreyfus Teacher-Scholar Awards Program. Supporting Information Available: Details of the synthesis, crystallization, X-ray and electrochemical analysis, and supporting Figure S1 and Table S1−S4. REFERENCES (1)

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