Structure and optical properties of Ag135Cu60 nanocluster incorporating an Ag135 fullerene wrapped by copper complexes

Structure and optical properties of Ag135Cu60 nanocluster incorporating an Ag135 fullerene wrapped by copper complexes | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Structure and optical properties of Ag 135 Cu 60 nanocluster incorporating an Ag 135 fullerene wrapped by copper complexes Shuxin Wang, Li Tang, Weinan Dong, Qikai Han, Bin Wang, Zhennan Wu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4346557/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 14 Jan, 2025 Read the published version in Nature Synthesis → Version 1 posted You are reading this latest preprint version Abstract We report the synthesis and crystal structure of Ag 135 Cu 60 (PET) 60 Cl 42 ( Ag 135 Cu 60 for short hereafter; PET = 2-phenylethanethiol) — the first example of a noble metal nanocluster incorporating a C 60 -like buckminsterfullerene moiety. Ag 135 Cu 60 was obtained by sodium borohydride reduction of a solution of AgCu-SR complexes, and its structure can be described as Ag 13 @Ag 42 @Ag 60 Ag 20 @Cl 12 @Cu 60 (PET) 60 Cl 30 . This layer-by-layer assembly leads to varying electron delocalization due to changes in metal bond lengths, giving Ag 135 Cu 60 both molecular and metallic properties leading to unusual power dependencies resulting from molecular-state-directed acoustic oscillations. This research inspires further exploration into customizable metal nanocluster structures and opens up new opportunities to study the influence of nanocluster structure on the metallic state. Physical sciences/Chemistry/Inorganic chemistry Physical sciences/Chemistry/Coordination chemistry Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Organic ligand-protected metal nanoclusters are of ongoing interest due to their fascinating structures and potential applications, 1-12 with the synthesis of a metal nanocluster incorporating a Buckministerfullerene-type motif a priority due to the intriguing physicochemical properties demonstrated by fullerene-like nanopolyhedra in other fields. 13-22 However, work towards this goal has long been frustrated by the inherent instability of fullerenes comprised of elements other than carbon. In recent decades, researchers have made significant advancements in developing materials containing all-metal fullerene topologies using s-block, p-block, and f-block metal elements, yet studies on ds-block transition metals remain lacking. 23-27 First proposed in 2004, the “golden fullerene” Au 32 remained elusive until 2019 when Wang et al. synthesized and characterized [Au 32 (Ph 3 P) 8 (dpa) 6 ](SbF 6 ) 2 , which relies on amine and phosphine ligands as protective agents. 20, 21 Subsequently, Sun et al. used an embedded cation template method to synthesize the all-metallic fullerene cluster [K@Au 12 Sb 20 ] 5- , which has a near-spherical icosahedral framework but is relatively unstable due to the lack of ligand protection. 19 Sun et al. constructed a nanocluster resembling C 60 by replacing each Ag triangle in Ag 180 nanocages with a carbon atom and connecting them along the edges of the quadrilateral. 22 Nevertheless, fully replicating the geometry of C 60 in a metal nanocluster shell and achieving the precise integration of metal atoms remains a significant challenge. Here, we report the synthesis and characterization of Ag 135 Cu 60 (PET) 60 Cl 42 (henceforth abbreviated to Ag 135 Cu 60 ), a nanocluster which incorporates a buckminsterfullerene (C 60 )-like silver kernel and was found to be stabilized by the flexibility of its ligands and synergy between its constituent metals. Ag 135 Cu 60 , which can be expressed as Ag 13 @Ag 42 @Ag 60 Ag 20 @Cl 12 @Cu 60 (PET) 60 Cl 30 , exhibited unprecedented optical absorption characteristics, a very small bandgap, and transient absorption (TA) spectroscopy data consistent with both molecular and metallic states. Ag 135 Cu 60 also demonstrated unusual power dependence, due to entanglement with acoustic phonons. These work opens up new avenues for research in nanoscience and nanotechnology, and is expected to lead to the development of advanced materials for various technological applications. Results Synthesis and Characterization. Ag 135 Cu 60 nanoclusters were prepared in a one-pot method 28 , 29 by reducing a solution of 4-CH 3 C 6 H 4 SO 3 Ag, CuCl 2 ·2H 2 O and PET in dichloromethane and methanol with NaBH 4 . After stirring for 12 hours, a reddish-brown solution was obtained which was concentrated to yield a reddish-brown solid. This solid was washed with n -hex and dissolved in a mixture of dichloromethane/hexane for crystallization (see Methods for details). Alkylthiolates (PET) were selected as ligands primarily because of their ability to mitigate static disorder and promote crystallization — such flexible outer ligands can fix the metal atoms in highly symmetric metal cores and obviate the disorder issues that have plagued X-ray diffraction (SC-XRD) studies of symmetric clusters protected by rigid aryl thiolate ligands. The formula of Ag 135 Cu 60 was confirmed through thermogravimetric analysis (TGA), which showed an experimental total weight loss of 35.05% (Supplementary Fig. 1), closely matching the theoretical loss of 34.60% determined via X-ray crystallography ( vide infra ). Energy dispersive X-ray spectrometry (EDX) elemental mapping and X-ray photoelectron spectra (XPS) of Ag 135 Cu 60 further confirmed the existence of the expected Ag, Cu, C, S, and Cl elements (Supplementary Figs. 2 and 3). Inductively coupled plasma (ICP) measurements were conducted to further validate the ratio of Ag/Cu in the bi-metallic Ag 135 Cu 60 nanoclusters; the results matched the theoretical value (i.e., 135/60 of Ag/Cu), again verifying the formula (Supplementary Table 1). Additionally, the Ag 3d 5/2 binding energies were determined to be 368.52 eV, with deconvolution showing peaks at 368.29 eV (Ag 0 ) and 368.62 eV (Ag + ) (Supplementary Fig. 3b). The area ratio of Ag + /Ag 0 for Ag 3d 5/2 was calculated to be 1.03, supporting the coexistence of Ag + and Ag 0 in the Ag 135 Cu 60 . 30 , 31 Additionally, the Cu 2p signals in the Ag 135 Cu 60 nanocluster (centered at 933.19 eV) closely resembled those of Cu(I)-SR complexes, indicating a nearly + 1 valence state of Cu atoms on the outermost shell of the nanocluster (Supplementary Fig. 3c). This comprehensive characterization confirmed the synthesis and composition of Ag 135 Cu 60 . Structure of Ag 135 Cu 60 (PET) 60 Cl 42 . Crystals of Ag 135 Cu 60 were analyzed using X-ray diffraction and found to consist of two complete molecules packed together with the tetragonal P4 2 /m space group (Supplementary Table 2, and Supplementary Fig. 4). Each Ag 135 Cu 60 comprises an Ag 13 @Ag 42 @Ag 80 silver core, a surface shell of Cu 60 (PET) 60 Cl 30 , and an intermediate layer of Cl 12 , making it the largest Ag-Cu alloy nanocluster known to date (Fig. 1 ). The axial thickness and equatorial diameter of the Ag 135 Cu 60 kernel are 1.88 and 2.18 nm, respectively (Fig. 1 and Supplementary Fig. 5). Overall, Ag 135 Cu 60 resembles a sphere, with the entire kernel having quasi-D 5 symmetry. Figure 2 dissects Ag 135 Cu 60 . The center comprises an Ag 13 icosahedron, a typical arrangement seen in gold, 32 silver, 33 palladium, 34 and platinum 35 nanoclusters (Fig. 2 a). Surrounding this inner shell is a 42-atom Mackay icosahedron (Fig. 2 b), with the third shell, depicted in Fig. 2 c and 2 d, consisting of a buckminsterfullerene (C 60 ) structure made of 60 silver atoms arranged in 12 pentagons, 20 hexagons, 60 vertices, and 90 sides. 36 This third shell can also be referred to as a quasi-truncated icosahedron due to almost perfect in the Ag-Ag bond lengths in the 12 pentagons and 20 hexagons (Fig. 2 c). Twenty additional Ag atoms are positioned at the center of each hexagon on the surface of the Ag 60 layer, each of which simultaneously adopts \(\mu\) 6 and \(\mu\) 3 coordinating modes to connect the Ag 60 shell with the second shell Ag 42 (Fig. 2 d, j). The three-layered architecture into which this set of 135 Ag atoms is structured is denoted by Ag 13 @Ag 42 @Ag 80 and resembles a Russian nesting doll. A fourth shell of 12 Cl atoms organized into a Cl 12 icosahedra completes the core structure of Ag 13 @Ag 42 @Ag 80 @Cl 12 (Fig. 2 e, f). This core structure resembles a Mackay-type three-shell icosahedron, the stability of which is attributed to its high sphericity and surface energy minimization per classical Wulff construction principles. 37 , 38 This was further demonstrated by monitoring the stability of Ag 135 Cu 60 with UV-vis spectra (Supplementary Fig. 6). A similar core-shell structure was also observed in the bimetallic Cu 43 Al 12 and monometal Cu 55 nanoclusters, having configurations of Cu@Cu 12 @Cu 30 @Al 12 and Cu@Cu 12 @Cu 30 @Cu 12 . 38 , 39 The 12 Cl ligands on the surface adopt \(\mu\) 6 -Cl-Ag 6 coordination modes (Fig. 2 k). The last shell comprises 60 Cu atoms configured as a truncated dodecahedron, (Fig. 2 g, h), which also belongs to the family of Archimedean solids. 14 Ag 135 Cu 60 exhibits distinctive bond characteristics. The average Ag-Ag distance in Ag 13 is 2.868 Å (Supplementary Fig. 7, I, and Supplementary Table 3), slightly shorter than the Ag-Ag bond length of bulk silver (2.889 Å), indicating metallic bond characteristics. The average Ag-Ag bond distances of the second and third layers are 2.952 and 2.973 Å, respectively, much longer than that of Ag 13 (Supplementary Fig. 7, II, III, and Supplementary Table 3). In addition, the Cu-Cu average distance in the Cu 60 shell is 3.313 Å (Supplementary Fig. 7, IV, and Supplementary Table 3). The Cl-Ag average bond lengths between the Cl 20 and Ag 42 , Cl 20 and Ag 60 shells are 2.734 and 2.930 Å, respectively, which are much longer than the normal Ag-Cl bond lengths (2.36 Å) (Supplementary Fig. 8, II-V, III-V, and Supplementary Table 4). Furthermore, the Ag-Ag/Ag-Cu bond lengths between the 1st and 2nd, 2nd and 3rd, 3rd and Cu 60 shells are 2.856, 2.873, and 3.107 Å, respectively (Supplementary Fig. 8, I-II, II-III, III-IV, and Supplementary Table 4). The presence of the Ag 60 fullerene in the Ag 135 Cu 60 structure emphasizes the ability of silver to replicate carbo-fullerene structures, and hints at a potential role for it in the design of more complex nanoclusters in the future. The 60 PET ligands and 30 Cl atoms on the surface of Ag 135 Cl 12 Cu 60 each adopt a specific coordination mode (Fig. 2 i, l, and m). The S atoms of PET exhibit a \(\mu\) 2 -Cu 2 , \(\mu\) 2 -Ag 2 four-coordinating mode, bridging the third shell Ag 60 and the fifth shell Cu 60 (Fig. 2 i, m). The average Cu-S and Ag-S bond lengths are 2.219 Å and 2.707 Å, respectively (Supplementary Fig. 9, and Supplementary Table 5). The 30 Cl atoms are coordinated with Cu in a \(\mu\) 2 -Cl-Cu 2 mode (Fig. 2 i, l), with an average Cu-Cl distance of 2.301 Å (Supplementary Fig. 9, and Supplementary Table 5). The Ag 135 Cu 60 crystal lattice is organized with an ABAB pattern (Supplementary Fig. 10). The coordination chemistry of the Ag 135 Cu 60 nanocluster, which involves PET ligands and Cl atoms, is crucial in connecting various metallic shells and ensuring structural stability. The specific coordination modes and bond lengths between the PET ligands (Cu-S and Ag-S) and the Cl atoms (Cu-Cl), in conjunction with the ABAB pattern of the crystal lattice, emphasize the intricate network of interactions that underlie the distinctive properties of the nanocluster. No counterions were detected in the single-crystal diffraction studies of the Ag 135 Cu 60 cluster, nor were signals in either the positive or negative ion modes in ESI, suggesting it to exist as a neutral molecule. Its electron spin-resonance (ESR) spectrum showed a single local maximum and minimum with a prominent signal at S = 1/2 (that is, g = 1.8485, 1.7863 (solid state); g = 1.8327, 1.7606 (solution state)) (Fig. 3 a, and Supplementary Fig. 11) — evidence of an unpaired electron, which suggests an open-shell electron configuration and is consistent with a calculated free electron count of 93 (n = 135 + 60–60–42 = 93). 40 Optical Absorption. The UV-vis spectra of Ag 135 Cu 60 exhibited multiple peaks at 407 nm, 500 nm, 643 nm, 731 nm, and 884 nm, with molecular absorbance coefficients (ε) of 4.8 x 10 4 M - 1 cm - 1 , 1.1 x 10 5 M - 1 cm - 1 , 1.5 x 10 5 M - 1 cm - 1 , 7.6 x 10 3 M - 1 cm - 1 and 3.1 x 10 3 M - 1 cm - 1 , respectively (Fig. 3 b). These values are significantly higher than those corresponding to the HOMO-LUMO transition of Au 25 (SR) 18 - (8.8 ×10 3 M - 1 cm - 1 ), 41 but slightly lower than that for the local surface plasmon (LSP) of Au ∼500 (SR) ∼120 (1.42 × 10 6 M - 1 cm - 1 ). 42 Of note, the absorption peak at 500 nm in Ag 135 Cu 60 is distinct from previously reported clusters with molecular states but similar to plasma absorption. 43 , 44 Electrochemical Properties. Differential pulse voltammetry (DPV) and cyclic voltammetry (CV) tests were conducted to further investigate the electrochemical properties of Ag 135 Cu 60 (Fig. 3 c and Supplementary Figs. 12, 13 and Supplementary Table 6). DPV data was consistent with Ag 135 Cu 60 having quantized double layer (QDL) charging with high consistent potential spacing (ΔV) values (about ± 5 mV) and near equispaced QDL charging waves, as detailed in Supplementary Figs. 11, 12 and Table 6. The capacitance of Ag 135 Cu 60 was calculated to be 1.14 aF by z-plot, less than that of Ag 307 (SR) 110 Cl 62 (1.39 aF) and consistent with the trend that the capacitance increases with nanocluster size (Fig. 3 d). 31 , 43 Cyclic voltammetry (CV) results showed the charging-discharging capability of Ag 135 Cu 60 to be good, with no changes in curve after 20 cycles noted (Supplementary Fig. 13). A potential spacing of 0.238 eV, which was larger than the rest, was assigned as the electrochemical gap (E g ) (Supplementary Table 6). 45 – 47 The charging energy for Ag 135 Cu 60 was determined to be 0.228 eV, based on the peak spacing immediately adjacent to the large gap. 46 This implies that Ag 135 Cu 60 has a minuscule “HOMO-LUMO” gap (E g = 0.238 − 0.228 = 0.01 eV) — reminiscent of Au 156 , which also exhibits both molecular and metallic behavior. 48 However, drawing definitive conclusions from DPV analyses can be difficult for clusters exhibiting both molecular and metallic behaviors due to the potential involvement of these states in separate electrochemical processes, leading to a complicated DPV signal that is impossible to interpret. Such complex systems necessitate further studies combined with other characterization methods such as transient absorption spectroscopy (TA) to definitively describe their electronic behavior. Ultrafast Electron Dynamics. Classifying Ag 135 Cu 60 as a metallic- and/or molecular- NC has important implications for understanding the structure-directed electronic behavior of metallic molecules. 49 – 51 The excited-state dynamics of Ag 135 Cu 60 were explored through femtosecond transient absorption spectrometry (fs-TA), where the initial electron temperature determines the whole relaxation in the metallic state while the single-electron transition model remains unaffected in the molecular state. 52 Three apparent ground-state bleaching (GSB) bands were detected upon 365 nm excitation at around 490 nm, 640 nm, and 725 nm, consistent with the steady-state absorption peaks. In addition, three excited state absorption (ESA) bands were captured near 550 nm, 600 nm, and 665 nm (Fig. 4 a, b). The 2D fs-TA spectra of Ag 135 Cu 60 showed similar features under different pump fluences (30, 21, 15, and 4 mW), other than a low-energy ESA band at 665 nm in 4 mW-pumped TA map, which could result from the weak scattering resistance of low-energy light (Supplementary Fig. 14a-c). Because the GSB overlaps with the broad ESA, the kinetic curve at 526 nm was first monitored to look for electron relaxation paths in upper energy levels. As shown in Fig. 4 c, the decay process was power dependent, but the next kinetic curve monitored at 615 nm was power independent and exhibited a completely different decay behavior from that at 526 nm (Fig. 4 d). The triexponential fitting results for the curve monitored at 526 nm are shown in Supplementary Fig. 15a-d: 0.42 ps, 5.6 ps, and 233.0 ps for 30 mW; 0.36 ps, 5.0 ps, and 207.6 ps for 21 mW; 0.34 ps, 4.8 ps, and 196.9 ps for 15 mW; and 0.27 ps, 4.4 ps, and 99.0 ps for 4 mW, where the positive correlation between the relaxation lifetimes and the increased electron temperature reflects the metallic nature of Ag 135 Cu 60 . The time constants at 1 ps were attributed to phonon-phonon coupling (Supplementary Fig. 15e). 48 While, the relatively fast processes affected most by the pump power at an initial time are kept unchanged for 615 nm, which suggests that Ag 135 Cu 60 possesses a molecular state. The ESA around 550 nm should be dominated by metallic states while the ESA near 600 nm could be dominated by molecular states. To our surprise, the positive correlation of ESA 550 nm-directed metallic state was weaker under 570 nm excitation (Fig. 4 e) and absent at 680 nm excitation (Fig. 4 f), even though a similar electronic relaxation path to that of 365 nm excitation (Supplementary Fig. 16–17). This abnormal power dependence compelled consideration of the possibility that the electrons were quenched by acoustic phonons, because distinct oscillatory behavior is detected in 2D-TA maps for 570 nm and 680 nm excitation. 53 A linear detection mode was used to investigate phonon dynamics within the initial few picoseconds (Supplementary Fig. 18–20); oscillatory signals at longer time scales and selected pump powers were not detected at 365 nm excitation. There are distinct vibrational features in the 2D fs-TA maps for 570 nm and 680 nm with higher pumping powers. The pure acoustic oscillations were extracted by subtracting the fitting electron dynamics, the decay traces at 533 nm for 570 nm excitation, and at 536 nm for 680 nm excitation (Fig. 4 g). The frequency and amplitude were then obtained through the Fourier transform (FFT) (Supplementary Fig. 21). The amplitude increases dramatically with increasing pump powers, which leads to faster electron loss under high-power excitation. This acoustic oscillation was absent at higher energy (365 nm) excitation; on the other hand, although 570 nm excitation produced a stronger amplitude than 680 nm, weaker electron quenching instead. Cryogenic optical absorption spectroscopy was used to study carry out fundamental studies of the electron-phonon interactions (Fig. 4 h). 54 – 56 Oscillator strengths increased significantly with decreasing temperature, but the 640 nm and 726 nm peaks were significantly different compared with the 500 nm peak, whose absorption features became sharper and whose absorption maxima shifted to higher energies. These results are consistent with the conclusion that the 500 nm peak corresponds mainly to a metallic state, and the 640 nm and 726 nm peaks to molecular states. The photoelectrons were predominantly absorbed by the electronic state upon 365 nm excitation and by the molecular state upon 570 nm and 680 nm excitation, giving rise to significant acoustic oscillations. The Bose-Einstein two-oscillator model (Eq. 1) was introduced to identify the relative contributions of acoustic phonons to the 640 nm and 726 nm absorption peaks. 57 E g (0) is the gap at 0 K, k B is the Boltzmann constant, T is the temperature in Kelvin, α is a constant, and ℏω OP and ℏω AP are the average energies for optical phonons and acoustic phonons, W 1 and W 2 are corresponding normalization constants. The contribution of the acoustic phonon to the absorption peak at 700 nm was more significant (i.e., W 2 = 0.29 for 640 nm peak, W 2 = 0.6 for 726 nm peak), suggesting stronger coupling ability (Fig. 4 i, j). Discussion We have reported the synthesis, structure, magnetism, photophysical properties, and electrochemical characteristics of the Ag 135 Cu 60 nanocluster, the first example of a nanocluster having a buckyball solid sphere structure composed of 135 silvers atoms. Ultrafast electron dynamics results revealed that this nanocluster exhibits both molecular and metallic states, providing experimental support for understanding the structure-oriented origin of plasmon resonance at the atomic scale. Methods Reagents. All chemicals including silver p -toluenesulfonate (4-CH 3 C 6 H 4 SO 3 Ag, 99.9%, metal basis), copper chloride (CuCl 2 ·2H 2 O, 99.99% metals basis), sodium borohydride (NaBH 4 , 99%), 2-phenylethylmercaptan (PET, C 8 H 10 S, 98%), methylene chloride (CH 2 Cl 2 , HPLC grade), methanol (CH 3 OH, HPLC grade), and n -hexane (Hex, HPLC grade), were purchased from Sigma‒Aldrich and used without further purification. Synthesis of Ag 135 Cu 60 (PET) 60 Cl 42 . CuCl 2 ·2H 2 O (40 mg) was added to a solution of 4-CH 3 C 6 H 4 SO 3 Ag (50 mg) in CH 3 OH (2 mL) and CH 2 Cl 2 (25 mL), prepared with sonication. The green suspension was vigorously stirred (1200 rpm) with a magnetic stir bar for 15 min. Then, PET (366 \(\mu \text{L}\) ) was added, and the reaction was vigorously stirred once again. After 30 minutes, the color of the solution changed from green to white. An ice-cold solution of NaBH 4 (50 mg) in water (2 mL) was quickly added to the solution, the color of which immediately darkened. The reaction was then kept under continuous stirring for 12 h. The mixture was concentrated in vacuo to give a reddish brown solid, which was washed with n -hexane three times to give Ag 135 Cu 60 (PET) 60 Cl 42 in a yield of 10% (Ag atom basis). The as-prepared nanocluster was crystallized in CH 2 Cl 2 / n -Hex at room temperature. Black crystals were obtained after approximately 5–7 days (Supplementary Fig. 22). X-ray crystallography. SC-XRD data was collected using a Bruker D8 QUEST X-ray single-crystal diffractometer irradiating with Mo Kα radiation (λ = 0.71073 Å) at 170K. The structure of Ag 135 Cu 60 (PET) 60 Cl 42 was solved using ShelXT via intrinsic phasing in Olex2. Subsequently, the full matrix least squares method was used to improve the structure of F 2 using SHELXTL software package. The CCDC number of Ag 135 Cu 60 (PET) 60 Cl 42 is 2307961. Characterization UV-Vis absorption spectra were acquired on a UV-8000 spectrophotometer. X-ray photoelectron spectroscopy (XPS) measurements were acquired on an ESCALAB XI + equipped with a flood gun to counter charging effects at an analysis chamber base pressure lower than 1 x 10 − 9 mbar with a monochromatic AlKα (1486.8 eV) 150 W X-ray source and 0.5 mm circular spot size. Scanning Electron Microscope (SEM) analysis was performed using an */S-4800 microscope, operating within an accelerating voltage range of 0.1–30 kV. Inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements were collected on an AtomScan Advantage instrument (Thermo Jerrell Ash Corporation). Electron paramagnetic resonance (EPR) spectra were collected on a Bruker EMX plus 10/12 equipped with an Oxford ESR910 Liquid Helium cryostat, at the High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei City. Electrochemical measurements were carried out on a CHI 660E electrochemical workstation (CHI Instruments) with a three-electrode system. The working electrode was a glassy carbon, a Ag/AgCl was used as the reference electrode and a Pt wire was used as the counter electrode in 0.1M Bu 4 NPF 6 at -72 o C (in ethanol/dry ice bath). All the solutions were degassed and blanketed with high-purity N 2 prior to and during measurement. Femtosecond-TA spectroscopy was performed on a commercial Ti: Sapphire laser system (Spitfire Spectra-Physics; 100 fs, 3.5 mJ, 1 kHz). Solution samples in 1 mm path length cuvettes were excited by the tunable output of the OPA (pump). Declarations Acknowledgements S.W. acknowledges the financial support provided by the National Natural Science Foundation of China (22171156 and 21803001), Taishan Scholar Foundation of Shandong Province (China), Shandong Province Excellent Youth Innovation Team and Startup Funds from Qingdao University of Science and Technology. Z.W. is financially supported by the National Science Foundation of China (12174151). EPR was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory, CAS. Author contributions L.T. and Q.H. carried out experiments, analyzed the data and wrote the manuscript. B.W. performed the electrochemical measurements. Z.W. and W.D. performed the fs-TA experiments, analyzed the fs-TA data and wrote the manuscript. S.W. designed the project, analyzed the data, and revised the manuscript. All authors commented on it. Competing interests The authors declare no competing interests. Additional information Supplementary information The online version contains supplementary material available at https:xxxx. Correspondence and requests for materials should be addressed to S. W. or Z. W. Peer review information Nature Synthesis thanks the anonymous reviewer(s) for their contribution to the peer review of this work. Reprints and permission information is available at http://www.xxxxx Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Data availability The Supporting Information is available free of charge at XXXX. References Chakraborty, I. & Pradeep, T. Atomically precise clusters of noble metals: emerging link between atoms and nanoparticles. Chem. Rev. 117, 8208–8271 (2017). Chen, T., Lin, H., Cao, Y., Yao, Q. & Xie, J. Interactions of metal nanoclusters with light: fundamentals and applications. Adv. Mater. 34, 2103918 (2021). Dong, C. et al. 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Temperature-dependent optical absorption properties of monolayer-protected Au 25 and Au 38 clusters. J. Phys. Chem. Lett. 2, 2752–2758 (2011). Devadas, M. S. et al. Temperature-dependent absorption and ultrafast luminescence dynamics of bi-icosahedral Au 25 clusters. J. Phys. Chem. C. 117, 23155–23161 (2013). Liu, Z. Y. et al. Observation of core phonon in electron-phonon coupling in Au 25 nanoclusters. J. Phys. Chem. Lett. 12, 1690–1695 (2021). Liu, Z. Y.et al. Tailoring the electron-phonon interaction in Au 25 (SR) 18 nanoclusters via ligand engineering and insight into luminescence. ACS Nano 16, 18448–18458 (2022). Additional Declarations There is NO Competing Interest. Supplementary Files supplementaryinformation.pdf Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 14 Jan, 2025 Read the published version in Nature Synthesis → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4346557","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":302446301,"identity":"21f17d11-13cb-4643-8d0a-d64dd917363c","order_by":0,"name":"Shuxin Wang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+klEQVRIiWNgGAWjYDACCSBOgDAZH0DFDIjWwmwA5ROhBQrYJIjSIj+7x0zi4Q6GxP7Z7dcq3rbV1TGwN2+TYKi5g1OLwZ0zxgaJZxgSZ9w5U3ZzbtthCQaeY2USDMee4dYikWP4ILGNIbfhRk7abd62AxIMEjlmEowNh3E7bEaOwQGQlvlALcW8bXUSDPJv8GthuAG1ZcON9GPMvG3MQFt48GsxuJFWbADUUr/xRg6z5JxzhyXbeNKKLRKO4XNY8jbJn20MxnI30h9+eFNWx8/PfnjjjQ81eBwGAf+BmMeAgQdIsYH4CYQ0QAD7A7CWUTAKRsEoGAXoAAAdSVKZTmPUrAAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0003-0403-3953","institution":"Qingdao University of Science and Technology","correspondingAuthor":true,"prefix":"","firstName":"Shuxin","middleName":"","lastName":"Wang","suffix":""},{"id":302446302,"identity":"177b2b86-802e-456b-982e-11346f5db10b","order_by":1,"name":"Li Tang","email":"","orcid":"","institution":"Qingdao University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Li","middleName":"","lastName":"Tang","suffix":""},{"id":302446303,"identity":"8bd7f6a7-3734-4306-8ced-dea45d3b3a7f","order_by":2,"name":"Weinan Dong","email":"","orcid":"","institution":"Qingdao University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Weinan","middleName":"","lastName":"Dong","suffix":""},{"id":302446304,"identity":"1ba700bd-2d62-449d-befa-2b9865fd3aa5","order_by":3,"name":"Qikai Han","email":"","orcid":"","institution":"Qingdao University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Qikai","middleName":"","lastName":"Han","suffix":""},{"id":302446305,"identity":"6cf22eea-2c55-4fe4-8448-c4613a00cf96","order_by":4,"name":"Bin Wang","email":"","orcid":"","institution":"Qingdao University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Bin","middleName":"","lastName":"Wang","suffix":""},{"id":302446306,"identity":"994e8d02-5866-46f6-819b-cf622afdaca9","order_by":5,"name":"Zhennan Wu","email":"","orcid":"","institution":"Qingdao University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Zhennan","middleName":"","lastName":"Wu","suffix":""}],"badges":[],"createdAt":"2024-04-30 06:00:31","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4346557/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4346557/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s44160-024-00723-1","type":"published","date":"2025-01-14T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":56541221,"identity":"5df4ee57-5c83-410b-9c0c-ea1d6ba92a37","added_by":"auto","created_at":"2024-05-15 14:25:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":131272,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMolecular structure of Ag\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e(PET)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e42\u003c/strong\u003e\u003c/sub\u003e. The dimension shown excludes the thickness of the ligand shell. Color labels: Purple, Ag; yellow, S; green/blue, Cl; gray, C. All hydrogen atoms are omitted for clarity.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/0f35721d3339d4d21b089757.png"},{"id":56541222,"identity":"7d7338b2-8e2f-4759-89fc-529c7607c3d9","added_by":"auto","created_at":"2024-05-15 14:25:21","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":599945,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDissection of the Ag\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e atomic structure.\u003c/strong\u003e (a) First shell: Ag\u003csub\u003e13 \u003c/sub\u003e(turquoise) Mackay icosahedron. (b) Second shell: Ag\u003csub\u003e42\u003c/sub\u003e (rose) Mackay icosahedron. (c) Third shell: Ag\u003csub\u003e60\u003c/sub\u003e-like-soccer alkene structure cage, with (d) one Ag atom (red) arranged on each of the hexagonal facets at the center of the Ag\u003csub\u003e60\u003c/sub\u003e shell (Ag\u003csub\u003e20\u003c/sub\u003e). (e) Fourth shell: Cl\u003csub\u003e12\u003c/sub\u003e (blue) icosahedral shell. (f) Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e80\u003c/sub\u003e@Cl\u003csub\u003e12\u003c/sub\u003e four-shell structure. (g) Fifth shell: Cu\u003csub\u003e60\u003c/sub\u003e (orange) truncated dodecahedron. (h) Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e80\u003c/sub\u003e@Cl\u003csub\u003e12\u003c/sub\u003e@Cu\u003csub\u003e60\u003c/sub\u003e five-shell structure. (i) Decoration of Ag\u003csub\u003e135\u003c/sub\u003e@Cu\u003csub\u003e60\u003c/sub\u003e with 30 Cl (green) and 60 S (yellow) atoms. (j), (k), (l), and (m) bonding modes of Cl/S with Ag/Cu.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/8fa4d6f2b1570e67d97b9d89.png"},{"id":56541220,"identity":"38c4a001-da5f-4513-aae3-f7f841aeaa8d","added_by":"auto","created_at":"2024-05-15 14:25:21","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":132465,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eComprehensive examination of the optical properties and electronic structure of\u003c/strong\u003e \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e \u003cstrong\u003enanocluster.\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e \u003c/strong\u003e\u003c/sub\u003e(a) Electron paramagnetic resonance (EPR) spectra of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e in solid state. (b) UV-vis absorption spectrum of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solution at room temperature. Insets are the photos of single crystals of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e and a photograph of nanoclusters dissolved in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e. (c) DPV of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003csub\u003e.\u003c/sub\u003e (d) z-plots of formal potentials of charging events versus cluster charge states (z) for \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e. Formal potentials were obtained from the DPV response in Fig. 3c.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/cda00017998c2531b1d2e7ed.png"},{"id":56542600,"identity":"cd7cac35-2e6e-4d77-821e-81752386cd90","added_by":"auto","created_at":"2024-05-15 14:33:21","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":292876,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eUltrafast transient absorption spectroscopy analysis of the Ag\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanocluster. \u003c/strong\u003e(a, b) Femtosecond-TA map and line-by-line TA spectra as a function of selected time delays from 1 ps to 1 ns under 365 nm excitation with pump power 30 mW. (c, d)\u003cstrong\u003e \u003c/strong\u003eSelected ESA kinetic decays for \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanocluster at 526 nm and 615 nm upon 365 nm excitation with different pump powers. (e, f) Selected ESA kinetic decays of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanocluster at 526 nm for 570 nm excitation and at 536 nm for 680 nm excitation. (g) Pure acoustic oscillations under 570 nm and 680 nm excitation with different pump powers. (h) Temperature-dependent absorption spectrum of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanocluster. The color from black to blue represents a decrease in temperature from 300 K to 120 K, 20 K gap. (i-j) Fitting results by the Bose-Einstein two-oscillator model.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/c6b6abdea20e7d681be351a3.png"},{"id":73840475,"identity":"ff1e2536-207b-4898-aa49-938e7046b469","added_by":"auto","created_at":"2025-01-15 08:10:06","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2306622,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/79db0eac-5267-4df3-9d6a-bf6bce1af76d.pdf"},{"id":56541224,"identity":"634d1b82-55ef-4741-8dc9-d1fd4b49eb94","added_by":"auto","created_at":"2024-05-15 14:25:21","extension":"pdf","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":2882495,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"supplementaryinformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4346557/v1/a4958c33185718d6354afd4c.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eStructure and optical properties of Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e nanocluster incorporating an Ag\u003csub\u003e135\u003c/sub\u003e fullerene wrapped by copper complexes\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eOrganic ligand-protected metal nanoclusters are of ongoing interest due to their fascinating structures and potential applications,\u003csup\u003e1-12\u003c/sup\u003e with the synthesis of a metal nanocluster incorporating a Buckministerfullerene-type motif a priority due to the intriguing physicochemical properties demonstrated by fullerene-like nanopolyhedra in other fields.\u003csup\u003e13-22\u003c/sup\u003e However, work towards this goal has long been frustrated by the inherent instability of fullerenes comprised of elements other than carbon.\u0026nbsp;In recent decades, researchers have made significant advancements in developing materials containing all-metal fullerene topologies using s-block, p-block, and f-block metal elements, yet studies on ds-block transition metals remain lacking.\u003csup\u003e23-27\u003c/sup\u003e First proposed in 2004, the \u0026ldquo;golden\u0026nbsp;fullerene\u0026rdquo; Au\u003csub\u003e32\u003c/sub\u003e remained elusive until 2019 when Wang et al. synthesized and characterized [Au\u003csub\u003e32\u003c/sub\u003e(Ph\u003csub\u003e3\u003c/sub\u003eP)\u003csub\u003e8\u003c/sub\u003e(dpa)\u003csub\u003e6\u003c/sub\u003e](SbF\u003csub\u003e6\u003c/sub\u003e)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e, which relies on amine and phosphine ligands as protective agents.\u003csup\u003e20, 21\u003c/sup\u003e Subsequently, Sun et al. used an embedded cation template method to synthesize the all-metallic fullerene cluster [K@Au\u003csub\u003e12\u003c/sub\u003eSb\u003csub\u003e20\u003c/sub\u003e]\u003csup\u003e5-\u003c/sup\u003e, which has a near-spherical icosahedral framework but is relatively unstable due to the lack of ligand protection.\u003csup\u003e19\u003c/sup\u003e Sun et al. constructed a nanocluster resembling C\u003csub\u003e60\u003c/sub\u003e by replacing each Ag triangle in Ag\u003csub\u003e180\u003c/sub\u003e nanocages with a carbon atom and connecting them along the edges of the quadrilateral.\u003csup\u003e22\u003c/sup\u003e Nevertheless, fully replicating the geometry of C\u003csub\u003e60\u003c/sub\u003e in a metal nanocluster shell and achieving the precise integration of metal atoms remains a significant challenge.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eHere, we report the synthesis and characterization of Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e42\u003c/sub\u003e (henceforth abbreviated to \u003cstrong\u003eAg\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e\u003c/strong\u003e), a nanocluster which incorporates a buckminsterfullerene (C\u003csub\u003e60\u003c/sub\u003e)-like silver kernel and was found to be stabilized by the flexibility of its ligands and synergy between its constituent metals. \u003cstrong\u003eAg\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e\u003c/strong\u003e, which can be expressed as Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e60\u003c/sub\u003eAg\u003csub\u003e20\u003c/sub\u003e@Cl\u003csub\u003e12\u003c/sub\u003e@Cu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e30\u003c/sub\u003e,\u0026nbsp;exhibited unprecedented optical absorption characteristics, a very small\u0026nbsp;bandgap, and\u0026nbsp;transient absorption (TA) spectroscopy data consistent with both molecular and metallic states. \u003cstrong\u003eAg\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e\u003c/strong\u003e also demonstrated unusual power dependence, due to entanglement with acoustic phonons. These work opens up new avenues for research in nanoscience and nanotechnology, and is expected to lead to the development of advanced materials for various technological applications.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eSynthesis and Characterization. Ag\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e nanoclusters were prepared in a one-pot method\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e by reducing a solution of 4-CH\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eSO\u003csub\u003e3\u003c/sub\u003eAg, CuCl\u003csub\u003e2\u003c/sub\u003e\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO and PET in dichloromethane and methanol with NaBH\u003csub\u003e4\u003c/sub\u003e. After stirring for 12 hours, a reddish-brown solution was obtained which was concentrated to yield a reddish-brown solid. This solid was washed with \u003cem\u003en\u003c/em\u003e-hex and dissolved in a mixture of dichloromethane/hexane for crystallization (see Methods for details). Alkylthiolates (PET) were selected as ligands primarily because of their ability to mitigate static disorder and promote crystallization \u0026mdash; such flexible outer ligands can fix the metal atoms in highly symmetric metal cores and obviate the disorder issues that have plagued X-ray diffraction (SC-XRD) studies of symmetric clusters protected by rigid aryl thiolate ligands. The formula of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e was confirmed through thermogravimetric analysis (TGA), which showed an experimental total weight loss of 35.05% (Supplementary Fig. 1), closely matching the theoretical loss of 34.60% determined via X-ray crystallography (\u003cem\u003evide infra\u003c/em\u003e). Energy dispersive X-ray spectrometry (EDX) elemental mapping and X-ray photoelectron spectra (XPS) of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e further confirmed the existence of the expected Ag, Cu, C, S, and Cl elements (Supplementary Figs. 2 and 3). Inductively coupled plasma (ICP) measurements were conducted to further validate the ratio of Ag/Cu in the bi-metallic \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanoclusters; the results matched the theoretical value (i.e., 135/60 of Ag/Cu), again verifying the formula (Supplementary Table 1). Additionally, the Ag 3d\u003csub\u003e5/2\u003c/sub\u003e binding energies were determined to be 368.52 eV, with deconvolution showing peaks at 368.29 eV (Ag\u003csup\u003e0\u003c/sup\u003e) and 368.62 eV (Ag\u003csup\u003e+\u003c/sup\u003e) (Supplementary Fig.\u0026nbsp;3b). The area ratio of Ag\u003csup\u003e+\u003c/sup\u003e/Ag\u003csup\u003e0\u003c/sup\u003e for Ag 3d\u003csub\u003e5/2\u003c/sub\u003e was calculated to be 1.03, supporting the coexistence of Ag\u003csup\u003e+\u003c/sup\u003e and Ag\u003csup\u003e0\u003c/sup\u003e in the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e Additionally, the Cu 2p signals in the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanocluster (centered at 933.19 eV) closely resembled those of Cu(I)-SR complexes, indicating a nearly\u0026thinsp;+\u0026thinsp;1 valence state of Cu atoms on the outermost shell of the nanocluster (Supplementary Fig. 3c). This comprehensive characterization confirmed the synthesis and composition of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eStructure of Ag\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003e(PET)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e42\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e. Crystals of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e were analyzed using X-ray diffraction and found to consist of two complete molecules packed together with the tetragonal P4\u003csub\u003e2\u003c/sub\u003e/m space group (Supplementary Table 2, and Supplementary Fig. 4). Each \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e comprises an Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e80\u003c/sub\u003e silver core, a surface shell of Cu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e30\u003c/sub\u003e, and an intermediate layer of Cl\u003csub\u003e12\u003c/sub\u003e, making it the largest Ag-Cu alloy nanocluster known to date (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). The axial thickness and equatorial diameter of the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e kernel are 1.88 and 2.18 nm, respectively (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Fig. 5). Overall, \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e resembles a sphere, with the entire kernel having quasi-D\u003csub\u003e5\u003c/sub\u003e symmetry.\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e dissects \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e. The center comprises an Ag\u003csub\u003e13\u003c/sub\u003e icosahedron, a typical arrangement seen in gold,\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e silver,\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e palladium,\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e and platinum\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e nanoclusters (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea). Surrounding this inner shell is a 42-atom Mackay icosahedron (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb), with the third shell, depicted in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec and \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed, consisting of a buckminsterfullerene (C\u003csub\u003e60\u003c/sub\u003e) structure made of 60 silver atoms arranged in 12 pentagons, 20 hexagons, 60 vertices, and 90 sides.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e This third shell can also be referred to as a quasi-truncated icosahedron due to almost perfect in the Ag-Ag bond lengths in the 12 pentagons and 20 hexagons (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec). Twenty additional Ag atoms are positioned at the center of each hexagon on the surface of the Ag\u003csub\u003e60\u003c/sub\u003e layer, each of which simultaneously adopts \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e6\u003c/sub\u003e and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e3\u003c/sub\u003e coordinating modes to connect the Ag\u003csub\u003e60\u003c/sub\u003e shell with the second shell Ag\u003csub\u003e42\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed, j). The three-layered architecture into which this set of 135 Ag atoms is structured is denoted by Ag\u003csub\u003e13\u003c/sub\u003e @Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e80\u003c/sub\u003e and resembles a Russian nesting doll. A fourth shell of 12 Cl atoms organized into a Cl\u003csub\u003e12\u003c/sub\u003e icosahedra completes the core structure of Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e80\u003c/sub\u003e@Cl\u003csub\u003e12\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee, f). This core structure resembles a Mackay-type three-shell icosahedron, the stability of which is attributed to its high sphericity and surface energy minimization per classical Wulff construction principles.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e This was further demonstrated by monitoring the stability of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e with UV-vis spectra (Supplementary Fig. 6). A similar core-shell structure was also observed in the bimetallic \u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e43\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eAl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e12\u003c/strong\u003e\u003c/sub\u003e and monometal \u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e55\u003c/strong\u003e\u003c/sub\u003e nanoclusters, having configurations of Cu@Cu\u003csub\u003e12\u003c/sub\u003e@Cu\u003csub\u003e30\u003c/sub\u003e@Al\u003csub\u003e12\u003c/sub\u003e and Cu@Cu\u003csub\u003e12\u003c/sub\u003e@Cu\u003csub\u003e30\u003c/sub\u003e@Cu\u003csub\u003e12\u003c/sub\u003e.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e The 12 Cl ligands on the surface adopt \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e6\u003c/sub\u003e-Cl-Ag\u003csub\u003e6\u003c/sub\u003e coordination modes (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ek). The last shell comprises 60 Cu atoms configured as a truncated dodecahedron, (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eg, h), which also belongs to the family of Archimedean solids.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e exhibits distinctive bond characteristics. The average Ag-Ag distance in Ag\u003csub\u003e13\u003c/sub\u003e is 2.868 \u0026Aring; (Supplementary Fig. 7, I, and Supplementary Table 3), slightly shorter than the Ag-Ag bond length of bulk silver (2.889 \u0026Aring;), indicating metallic bond characteristics. The average Ag-Ag bond distances of the second and third layers are 2.952 and 2.973 \u0026Aring;, respectively, much longer than that of Ag\u003csub\u003e13\u003c/sub\u003e (Supplementary Fig. 7, II, III, and Supplementary Table 3). In addition, the Cu-Cu average distance in the Cu\u003csub\u003e60\u003c/sub\u003e shell is 3.313 \u0026Aring; (Supplementary Fig. 7, IV, and Supplementary Table 3). The Cl-Ag average bond lengths between the Cl\u003csub\u003e20\u003c/sub\u003e and Ag\u003csub\u003e42\u003c/sub\u003e, Cl\u003csub\u003e20\u003c/sub\u003e and Ag\u003csub\u003e60\u003c/sub\u003e shells are 2.734 and 2.930 \u0026Aring;, respectively, which are much longer than the normal Ag-Cl bond lengths (2.36 \u0026Aring;) (Supplementary Fig. 8, II-V, III-V, and Supplementary Table 4). Furthermore, the Ag-Ag/Ag-Cu bond lengths between the 1st and 2nd, 2nd and 3rd, 3rd and Cu\u003csub\u003e60\u003c/sub\u003e shells are 2.856, 2.873, and 3.107 \u0026Aring;, respectively (Supplementary Fig. 8, I-II, II-III, III-IV, and Supplementary Table 4). The presence of the Ag\u003csub\u003e60\u003c/sub\u003e fullerene in the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e structure emphasizes the ability of silver to replicate carbo-fullerene structures, and hints at a potential role for it in the design of more complex nanoclusters in the future.\u003c/p\u003e\n\u003cp\u003eThe 60 PET ligands and 30 Cl atoms on the surface of Ag\u003csub\u003e135\u003c/sub\u003eCl\u003csub\u003e12\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e each adopt a specific coordination mode (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ei, l, and m). The S atoms of PET exhibit a \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e-Cu\u003csub\u003e2\u003c/sub\u003e, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e-Ag\u003csub\u003e2\u003c/sub\u003e four-coordinating mode, bridging the third shell Ag\u003csub\u003e60\u003c/sub\u003e and the fifth shell Cu\u003csub\u003e60\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ei, m). The average Cu-S and Ag-S bond lengths are 2.219 \u0026Aring; and 2.707 \u0026Aring;, respectively (Supplementary Fig. 9, and Supplementary Table 5). The 30 Cl atoms are coordinated with Cu in a \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu\\)\u003c/span\u003e\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e-Cl-Cu\u003csub\u003e2\u003c/sub\u003e mode (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ei, l), with an average Cu-Cl distance of 2.301 \u0026Aring; (Supplementary Fig. 9, and Supplementary Table 5). The \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e crystal lattice is organized with an ABAB pattern (Supplementary Fig. 10). The coordination chemistry of the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e nanocluster, which involves PET ligands and Cl atoms, is crucial in connecting various metallic shells and ensuring structural stability. The specific coordination modes and bond lengths between the PET ligands (Cu-S and Ag-S) and the Cl atoms (Cu-Cl), in conjunction with the ABAB pattern of the crystal lattice, emphasize the intricate network of interactions that underlie the distinctive properties of the nanocluster.\u003c/p\u003e\n\u003cp\u003eNo counterions were detected in the single-crystal diffraction studies of the \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e cluster, nor were signals in either the positive or negative ion modes in ESI, suggesting it to exist as a neutral molecule. Its electron spin-resonance (ESR) spectrum showed a single local maximum and minimum with a prominent signal at S\u0026thinsp;=\u0026thinsp;1/2 (that is, g\u0026thinsp;=\u0026thinsp;1.8485, 1.7863 (solid state); g\u0026thinsp;=\u0026thinsp;1.8327, 1.7606 (solution state)) (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea, and Supplementary Fig.\u0026nbsp;11) \u0026mdash; evidence of an unpaired electron, which suggests an open-shell electron configuration and is consistent with a calculated free electron count of 93 (n\u0026thinsp;=\u0026thinsp;135\u0026thinsp;+\u0026thinsp;60\u0026ndash;60\u0026ndash;42\u0026thinsp;=\u0026thinsp;93).\u003csup\u003e40\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eOptical Absorption.\u003c/strong\u003e The UV-vis spectra of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e exhibited multiple peaks at 407 nm, 500 nm, 643 nm, 731 nm, and 884 nm, with molecular absorbance coefficients (\u0026epsilon;) of 4.8 x 10\u003csup\u003e4\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e cm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, 1.1 x 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e cm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, 1.5 x 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e cm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, 7.6 x 10\u003csup\u003e3\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e cm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e and 3.1 x 10\u003csup\u003e3\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e cm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, respectively (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb). These values are significantly higher than those corresponding to the HOMO-LUMO transition of Au\u003csub\u003e25\u003c/sub\u003e(SR)\u003csub\u003e18\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e (8.8 \u0026times;10\u003csup\u003e3\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003ecm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e),\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e but slightly lower than that for the local surface plasmon (LSP) of Au\u003csub\u003e\u0026sim;500\u003c/sub\u003e(SR)\u003csub\u003e\u0026sim;120\u003c/sub\u003e (1.42 \u0026times; 10\u003csup\u003e6\u003c/sup\u003e M\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003ecm\u003csup\u003e-\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e Of note, the absorption peak at 500 nm in \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e is distinct from previously reported clusters with molecular states but similar to plasma absorption.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e43\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eElectrochemical Properties.\u003c/strong\u003e Differential pulse voltammetry (DPV) and cyclic voltammetry (CV) tests were conducted to further investigate the electrochemical properties of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec and Supplementary Figs. 12, 13 and Supplementary Table 6). DPV data was consistent with \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e having quantized double layer (QDL) charging with high consistent potential spacing (\u0026Delta;V) values (about\u0026thinsp;\u0026plusmn;\u0026thinsp;5 mV) and near equispaced QDL charging waves, as detailed in Supplementary Figs. 11, 12 and Table 6. The capacitance of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e was calculated to be 1.14 aF by z-plot, less than that of Ag\u003csub\u003e307\u003c/sub\u003e(SR)\u003csub\u003e110\u003c/sub\u003eCl\u003csub\u003e62\u003c/sub\u003e (1.39 aF) and consistent with the trend that the capacitance increases with nanocluster size (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e Cyclic voltammetry (CV) results showed the charging-discharging capability of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e to be good, with no changes in curve after 20 cycles noted (Supplementary Fig. 13). A potential spacing of 0.238 eV, which was larger than the rest, was assigned as the electrochemical gap (E\u003csub\u003eg\u003c/sub\u003e) (Supplementary Table\u0026nbsp;6).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e45\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e The charging energy for \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e was determined to be 0.228 eV, based on the peak spacing immediately adjacent to the large gap.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e This implies that \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e has a minuscule \u0026ldquo;HOMO-LUMO\u0026rdquo; gap (E\u003csub\u003eg\u003c/sub\u003e = 0.238\u0026thinsp;\u0026minus;\u0026thinsp;0.228\u0026thinsp;=\u0026thinsp;0.01 eV) \u0026mdash; reminiscent of Au\u003csub\u003e156\u003c/sub\u003e, which also exhibits both molecular and metallic behavior.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e However, drawing definitive conclusions from DPV analyses can be difficult for clusters exhibiting both molecular and metallic behaviors due to the potential involvement of these states in separate electrochemical processes, leading to a complicated DPV signal that is impossible to interpret. Such complex systems necessitate further studies combined with other characterization methods such as transient absorption spectroscopy (TA) to definitively describe their electronic behavior.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eUltrafast Electron Dynamics.\u003c/strong\u003e Classifying \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e as a metallic- and/or molecular- NC has important implications for understanding the structure-directed electronic behavior of metallic molecules.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e The excited-state dynamics of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e were explored through femtosecond transient absorption spectrometry (fs-TA), where the initial electron temperature determines the whole relaxation in the metallic state while the single-electron transition model remains unaffected in the molecular state.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e Three apparent ground-state bleaching (GSB) bands were detected upon 365 nm excitation at around 490 nm, 640 nm, and 725 nm, consistent with the steady-state absorption peaks. In addition, three excited state absorption (ESA) bands were captured near 550 nm, 600 nm, and 665 nm (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea, b). The 2D fs-TA spectra of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e showed similar features under different pump fluences (30, 21, 15, and 4 mW), other than a low-energy ESA band at 665 nm in 4 mW-pumped TA map, which could result from the weak scattering resistance of low-energy light (Supplementary Fig. 14a-c). Because the GSB overlaps with the broad ESA, the kinetic curve at 526 nm was first monitored to look for electron relaxation paths in upper energy levels. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec, the decay process was power dependent, but the next kinetic curve monitored at 615 nm was power independent and exhibited a completely different decay behavior from that at 526 nm (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed). The triexponential fitting results for the curve monitored at 526 nm are shown in Supplementary Fig. 15a-d: 0.42 ps, 5.6 ps, and 233.0 ps for 30 mW; 0.36 ps, 5.0 ps, and 207.6 ps for 21 mW; 0.34 ps, 4.8 ps, and 196.9 ps for 15 mW; and 0.27 ps, 4.4 ps, and 99.0 ps for 4 mW, where the positive correlation between the relaxation lifetimes and the increased electron temperature reflects the metallic nature of \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e. The time constants at \u0026lt;\u0026thinsp;1 ps was assigned to electron-electron scattering according to the metallic state model; values of the order of a few picoseconds were attributed to electron-phonon coupling; those\u0026thinsp;\u0026gt;\u0026thinsp;1 ps were attributed to phonon-phonon coupling (Supplementary Fig.\u0026nbsp;15e).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e While, the relatively fast processes affected most by the pump power at an initial time are kept unchanged for 615 nm, which suggests that \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e possesses a molecular state. The ESA around 550 nm should be dominated by metallic states while the ESA near 600 nm could be dominated by molecular states. To our surprise, the positive correlation of ESA 550 nm-directed metallic state was weaker under 570 nm excitation (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee) and absent at 680 nm excitation (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ef), even though a similar electronic relaxation path to that of 365 nm excitation (Supplementary Fig.\u0026nbsp;16\u0026ndash;17).\u003c/p\u003e\n\u003cp\u003eThis abnormal power dependence compelled consideration of the possibility that the electrons were quenched by acoustic phonons, because distinct oscillatory behavior is detected in 2D-TA maps for 570 nm and 680 nm excitation.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e A linear detection mode was used to investigate phonon dynamics within the initial few picoseconds (Supplementary Fig. 18\u0026ndash;20); oscillatory signals at longer time scales and selected pump powers were not detected at 365 nm excitation. There are distinct vibrational features in the 2D fs-TA maps for 570 nm and 680 nm with higher pumping powers. The pure acoustic oscillations were extracted by subtracting the fitting electron dynamics, the decay traces at 533 nm for 570 nm excitation, and at 536 nm for 680 nm excitation (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eg). The frequency and amplitude were then obtained through the Fourier transform (FFT) (Supplementary Fig.\u0026nbsp;21). The amplitude increases dramatically with increasing pump powers, which leads to faster electron loss under high-power excitation. This acoustic oscillation was absent at higher energy (365 nm) excitation; on the other hand, although 570 nm excitation produced a stronger amplitude than 680 nm, weaker electron quenching instead.\u003c/p\u003e\n\u003cp\u003eCryogenic optical absorption spectroscopy was used to study carry out fundamental studies of the electron-phonon interactions (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eh).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e Oscillator strengths increased significantly with decreasing temperature, but the 640 nm and 726 nm peaks were significantly different compared with the 500 nm peak, whose absorption features became sharper and whose absorption maxima shifted to higher energies. These results are consistent with the conclusion that the 500 nm peak corresponds mainly to a metallic state, and the 640 nm and 726 nm peaks to molecular states. The photoelectrons were predominantly absorbed by the electronic state upon 365 nm excitation and by the molecular state upon 570 nm and 680 nm excitation, giving rise to significant acoustic oscillations. The Bose-Einstein two-oscillator model (Eq. 1) was introduced to identify the relative contributions of acoustic phonons to the 640 nm and 726 nm absorption peaks.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cimg src=\"data:image/png;base64,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\" width=\"444\" height=\"113\"\u003e\u003c/div\u003e\n\u003cp\u003e\u003cem\u003eE\u003c/em\u003e \u003csub\u003e\u0026nbsp;\u003cem\u003eg\u003c/em\u003e\u0026nbsp;\u003c/sub\u003e(0) is the gap at 0 K, \u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eB\u003c/em\u003e\u003c/sub\u003e is the Boltzmann constant, \u003cem\u003eT\u003c/em\u003e is the temperature in Kelvin, \u003cem\u003e\u0026alpha;\u003c/em\u003e is a constant, and ℏ\u0026omega;\u003csub\u003eOP\u003c/sub\u003e and ℏ\u0026omega;\u003csub\u003eAP\u003c/sub\u003e are the average energies for optical phonons and acoustic phonons, \u003cem\u003eW\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e and \u003cem\u003eW\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e are corresponding normalization constants. The contribution of the acoustic phonon to the absorption peak at 700 nm was more significant (i.e., W\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.29 for 640 nm peak, W\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.6 for 726 nm peak), suggesting stronger coupling ability (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ei, j).\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eWe have reported the synthesis, structure, magnetism, photophysical properties, and electrochemical characteristics of the \u003cb\u003eAg\u003c/b\u003e\u003csub\u003e\u003cb\u003e135\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eCu\u003c/b\u003e\u003csub\u003e\u003cb\u003e60\u003c/b\u003e\u003c/sub\u003e nanocluster, the first example of a nanocluster having a buckyball solid sphere structure composed of 135 silvers atoms. Ultrafast electron dynamics results revealed that this nanocluster exhibits both molecular and metallic states, providing experimental support for understanding the structure-oriented origin of plasmon resonance at the atomic scale.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eReagents.\u003c/b\u003e All chemicals including silver \u003cem\u003ep\u003c/em\u003e-toluenesulfonate (4-CH\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eSO\u003csub\u003e3\u003c/sub\u003eAg, 99.9%, metal basis), copper chloride (CuCl\u003csub\u003e2\u003c/sub\u003e\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO, 99.99% metals basis), sodium borohydride (NaBH\u003csub\u003e4\u003c/sub\u003e, 99%), 2-phenylethylmercaptan (PET, C\u003csub\u003e8\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003eS, 98%), methylene chloride (CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, HPLC grade), methanol (CH\u003csub\u003e3\u003c/sub\u003eOH, HPLC grade), and \u003cem\u003en\u003c/em\u003e-hexane (Hex, HPLC grade), were purchased from Sigma‒Aldrich and used without further purification.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of Ag\u003c/b\u003e \u003csub\u003e \u003cb\u003e135\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eCu\u003c/b\u003e \u003csub\u003e \u003cb\u003e60\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(PET)\u003c/b\u003e \u003csub\u003e \u003cb\u003e60\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eCl\u003c/b\u003e \u003csub\u003e \u003cb\u003e42\u003c/b\u003e \u003c/sub\u003e. CuCl\u003csub\u003e2\u003c/sub\u003e\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO (40 mg) was added to a solution of 4-CH\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eSO\u003csub\u003e3\u003c/sub\u003eAg (50 mg) in CH\u003csub\u003e3\u003c/sub\u003eOH (2 mL) and CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (25 mL), prepared with sonication. The green suspension was vigorously stirred (1200 rpm) with a magnetic stir bar for 15 min. Then, PET (366 \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\mu \\text{L}\\)\u003c/span\u003e\u003c/span\u003e) was added, and the reaction was vigorously stirred once again. After 30 minutes, the color of the solution changed from green to white. An ice-cold solution of NaBH\u003csub\u003e4\u003c/sub\u003e (50 mg) in water (2 mL) was quickly added to the solution, the color of which immediately darkened. The reaction was then kept under continuous stirring for 12 h. The mixture was concentrated in vacuo to give a reddish brown solid, which was washed with \u003cem\u003en\u003c/em\u003e-hexane three times to give Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e42\u003c/sub\u003e in a yield of 10% (Ag atom basis). The as-prepared nanocluster was crystallized in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/\u003cem\u003en\u003c/em\u003e-Hex at room temperature. Black crystals were obtained after approximately 5\u0026ndash;7 days (Supplementary Fig.\u0026nbsp;22).\u003c/p\u003e \u003cp\u003e \u003cb\u003eX-ray crystallography.\u003c/b\u003e SC-XRD data was collected using a Bruker D8 QUEST X-ray single-crystal diffractometer irradiating with Mo Kα radiation (λ\u0026thinsp;=\u0026thinsp;0.71073 \u0026Aring;) at 170K. The structure of Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e42\u003c/sub\u003e was solved using ShelXT via intrinsic phasing in Olex2. Subsequently, the full matrix least squares method was used to improve the structure of F\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e using SHELXTL software package. The CCDC number of Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e42\u003c/sub\u003e is 2307961.\u003c/p\u003e \u003cp\u003e \u003cb\u003eCharacterization\u003c/b\u003e UV-Vis absorption spectra were acquired on a UV-8000 spectrophotometer. X-ray photoelectron spectroscopy (XPS) measurements were acquired on an ESCALAB XI\u0026thinsp;+\u0026thinsp;equipped with a flood gun to counter charging effects at an analysis chamber base pressure lower than 1 x 10\u003csup\u003e\u0026minus;\u0026thinsp;9\u003c/sup\u003e mbar with a monochromatic AlKα (1486.8 eV) 150 W X-ray source and 0.5 mm circular spot size. Scanning Electron Microscope (SEM) analysis was performed using an */S-4800 microscope, operating within an accelerating voltage range of 0.1\u0026ndash;30 kV. Inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements were collected on an AtomScan Advantage instrument (Thermo Jerrell Ash Corporation). Electron paramagnetic resonance (EPR) spectra were collected on a Bruker EMX plus 10/12 equipped with an Oxford ESR910 Liquid Helium cryostat, at the High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei City. Electrochemical measurements were carried out on a CHI 660E electrochemical workstation (CHI Instruments) with a three-electrode system. The working electrode was a glassy carbon, a Ag/AgCl was used as the reference electrode and a Pt wire was used as the counter electrode in 0.1M Bu\u003csub\u003e4\u003c/sub\u003eNPF\u003csub\u003e6\u003c/sub\u003e at -72 \u003csup\u003eo\u003c/sup\u003eC (in ethanol/dry ice bath). All the solutions were degassed and blanketed with high-purity N\u003csub\u003e2\u003c/sub\u003e prior to and during measurement. Femtosecond-TA spectroscopy was performed on a commercial Ti: Sapphire laser system (Spitfire Spectra-Physics; 100 fs, 3.5 mJ, 1 kHz). Solution samples in 1 mm path length cuvettes were excited by the tunable output of the OPA (pump).\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eS.W. acknowledges the financial support provided by the National Natural Science Foundation of China (22171156 and 21803001), Taishan Scholar Foundation of Shandong Province (China), Shandong Province Excellent Youth Innovation Team and Startup Funds from Qingdao University of Science and Technology. Z.W. is financially supported by the National Science Foundation of China (12174151). EPR was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory, CAS.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eL.T. and Q.H. carried out experiments, analyzed the data and wrote the manuscript. B.W. performed the\u0026nbsp;electrochemical measurements. Z.W. and W.D. performed the fs-TA experiments, analyzed the fs-TA data and wrote the manuscript. S.W. designed the project, analyzed the data, and revised the manuscript. All authors commented on it.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupplementary information The online version contains supplementary material available at https:xxxx.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorrespondence\u0026nbsp;\u003c/strong\u003eand requests for materials should be addressed to S. W. or Z. W.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePeer review information\u0026nbsp;\u003c/strong\u003e\u003cem\u003eNature Synthesis\u003c/em\u003e thanks the anonymous reviewer(s) for\u003c/p\u003e\n\u003cp\u003etheir contribution to the peer review of this work.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eReprints and permission information\u003c/strong\u003e is available at http://www.xxxxx\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePublisher\u0026rsquo;s note\u003c/strong\u003e Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe Supporting Information is available free of charge at XXXX.\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eChakraborty, I. \u0026amp; Pradeep, T. 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Nanosized (\u0026micro;\u003csub\u003e12\u003c/sub\u003e-Pt)Pd\u003csub\u003e164-\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003ePt\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003e(CO)\u003csub\u003e72\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e20\u003c/sub\u003e (\u003cem\u003ex\u003c/em\u003e\u0026thinsp;\u0026asymp;\u0026thinsp;7) containing Pt-centered four-shell 165-atom Pd-Pt core with unprecedented intershell bridging carbonyl ligands: comparative analysis of icosahedral shell-growth patterns with geometrically related Pd\u003csub\u003e145\u003c/sub\u003e(CO)\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003e(PEt\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e30\u003c/sub\u003e (\u003cem\u003ex\u003c/em\u003e\u0026thinsp;\u0026asymp;\u0026thinsp;60) containing capped three-shell Pd\u003csub\u003e145\u003c/sub\u003e core. J. Am. Chem. 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ACS Nano 16, 18448\u0026ndash;18458 (2022).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4346557/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4346557/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eWe report the synthesis and crystal structure of Ag\u003csub\u003e135\u003c/sub\u003eCu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e42\u003c/sub\u003e (\u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e for short hereafter; PET = 2-phenylethanethiol) — the first example of a noble metal nanocluster incorporating a C\u003csub\u003e60\u003c/sub\u003e-like buckminsterfullerene moiety. \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e was obtained by sodium borohydride reduction of a solution of AgCu-SR complexes, and its structure can be described as Ag\u003csub\u003e13\u003c/sub\u003e@Ag\u003csub\u003e42\u003c/sub\u003e@Ag\u003csub\u003e60\u003c/sub\u003eAg\u003csub\u003e20\u003c/sub\u003e@Cl\u003csub\u003e12\u003c/sub\u003e@Cu\u003csub\u003e60\u003c/sub\u003e(PET)\u003csub\u003e60\u003c/sub\u003eCl\u003csub\u003e30\u003c/sub\u003e. This layer-by-layer assembly leads to varying electron delocalization due to changes in metal bond lengths, giving \u003cstrong\u003eAg\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e135\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCu\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e both molecular and metallic properties leading to unusual power dependencies resulting from molecular-state-directed acoustic oscillations. This research inspires further exploration into customizable metal nanocluster structures and opens up new opportunities to study the influence of nanocluster structure on the metallic state.\u003c/p\u003e","manuscriptTitle":"Structure and optical properties of Ag135Cu60 nanocluster incorporating an Ag135 fullerene wrapped by copper complexes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-05-15 14:25:16","doi":"10.21203/rs.3.rs-4346557/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-synthesis","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"natsynth","sideBox":"Learn more about [Nature Synthesis](https://www.nature.com/natsynth/)","snPcode":"","submissionUrl":"https://mts-natsynth.nature.com/cgi-bin/main.plex","title":"Nature Synthesis","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Research","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"91149a33-1028-4edd-a5b9-6c649219d72f","owner":[],"postedDate":"May 15th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":31930694,"name":"Physical sciences/Chemistry/Inorganic chemistry"},{"id":31930695,"name":"Physical sciences/Chemistry/Coordination chemistry"}],"tags":[],"updatedAt":"2025-01-15T08:10:00+00:00","versionOfRecord":{"articleIdentity":"rs-4346557","link":"https://doi.org/10.1038/s44160-024-00723-1","journal":{"identity":"nature-synthesis","isVorOnly":false,"title":"Nature Synthesis"},"publishedOn":"2025-01-14 05:00:00","publishedOnDateReadable":"January 14th, 2025"},"versionCreatedAt":"2024-05-15 14:25:16","video":"","vorDoi":"10.1038/s44160-024-00723-1","vorDoiUrl":"https://doi.org/10.1038/s44160-024-00723-1","workflowStages":[]},"version":"v1","identity":"rs-4346557","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4346557","identity":"rs-4346557","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}