Silver Sites Research Articles

Two-Dimensional Silver-Isocyanide Frameworks.

Metal-organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom-metal coordination dominates the MOFs community, and the rational synthesis of carbon-metal coordination-based MOFs remains a significant challenge. Herein, two-dimensional (2D) MOFs based on silver-carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide-based monomers at ambient condition. The as-synthesized 2D MOFs possess well-defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π-π stacking between layers, exhibit narrow band gaps down to 1.42 eV. As electrochemical catalysts for converting CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92 %. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand-to-metal charge-transfer effect. This work not only paves the way toward a new family of MOFs based on metal-isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.

Two‐Dimensional Silver–Isocyanide Frameworks

AbstractMetal–organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom‐metal coordination dominates the MOFs community, and the rational synthesis of carbon–metal coordination‐based MOFs remains a significant challenge. Herein, two‐dimensional (2D) MOFs based on silver–carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide‐based monomers at ambient condition. The as‐synthesized 2D MOFs possess well‐defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π–π stacking between layers, exhibit narrow band gaps down to 1.42 eV. As electrochemical catalysts for converting CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92 %. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand‐to‐metal charge–transfer effect. This work not only paves the way toward a new family of MOFs based on metal–isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.

Installation of Copper(I) and Silver(I) Sites into TREN-Based Porous Organic Cages via Postsynthetic Metalation.

Porous organic cages (POCs) and metal-organic polyhedra (MOPs) function as zero-dimensional porous materials, able to mimic many functions of insoluble framework materials while offering processability advantages. A popular approach to access tailored metal-based motifs in extended network materials is postsynthetic metalation, which allows metal installation to be decoupled from framework assembly. Surprisingly, this approach has only sparingly been reported for molecular porous materials. In this report, we demonstrate postsynthetic metalation of tetrahedral [4 + 4] POCs assembled from tris(2-aminoethyl)amine (TREN) and 1,3,5-tris(4-formylphenyl)benzene. The trigonally symmetric TREN motif is a common chelator in coordination chemistry and, in the POCs explored herein, readily binds copper(I) and silver(I) to form cationic cages bearing discrete mononuclear coordination fragments. Metalation retains cage porosity, allowing us to compare the sorption properties of the parent organic and metalated cages. Interestingly, introduction of copper(I) facilitates activated oxygen chemisorption, demonstrating how targeted metalation can be exploited to tune the sorption characteristics of porous molecular materials.

Highly efficient purification of long-chain alkenones using silver dimercaptotriazine flash chromatography

Long-chain alkenones (LCAs) are important tools for paleotemperature reconstructions in lacustrine and marine environments. However, some neutral lipid compounds that co-elute with LCAs often occur in natural sediment samples, which seriously interferes with the identification and quantification of the LCAs. In this study, we report a new flash column chromatography based on silver(I)-dimercaptotriazine (Ag-DMT) functionalized silica material (≡Si-DMT-Ag) for purifying and isolating the individual LCAs from complex lake and marine sediment samples. Compared to silver(I)-mercaptopropyl (Ag-MP) functionalized (≡Si-(CH2)3-S-Ag) and silver nitrate (SiO2 + AgNO3) impregnated silica materials used by previous studies, the Ag-DMT stationary phase displays the best efficiency in removing co-eluting compounds (including wax ester, hopanoid, hopanoic acid, sterane, alkanoic acid, and some unknown compounds) from the LCAs in our study lake and marine sediment samples. The Ag-DMT material also shows its high retention capacity for the LCAs, probably due to a strong interaction of more positively charged silver sites on Ag-DMT with double bonds. Employing the Ag-DMT chromatography, we develop an optimal solvent elution scheme to efficiently isolate the individual LCAs with the same chain length but different numbers of unsaturation for their isotopic analysis in the future. Our study provides a highly effective method for eliminating co-eluting compounds and isolating individual LCAs for paleoclimate studies.

Influence of Ag particle size and Ag : Al2O3 surface ratio in catalysts for the chloride-promoted ethylene epoxidation

Ethylene epoxidation is catalyzed by α-alumina supported silver catalysts. The influence of silver particle size has been a topic of debate, and was typically investigated without the industrially essential chloride promoter. We studied the catalyst behavior in the presence of chloride. Transient behavior was observed in the first tens of hours on stream, not as a result of particle growth, but due to the gradual change in the nature of the active silver site in the presence of chloride. Different strategies were used to tune the particle size: either varying the silver loading or varying the decomposition atmosphere. Increasing the particle size from 13 to 50 nm by changing the Ag loading from 2 to 15 wt% increased the selectivity from 35 to 80%. However, increasing the 15 wt% Ag particle size from 48 to 184 nm by varying the heat treatment led to a decrease in selectivity from 80 to 50%. Changing the Ag particle size with both strategies also changes the Ag : Al2O3 surface ratio. The ethylene oxide selectivity is actually correlated to the Ag : Al2O3 surface ratio, rather than to the particle size in this size range. This can be explained by its influence on the probability of a formed ethylene oxide molecule to subsequently further react over support surface groups.

Dicarboxylic Acids Induced Tandem Transformation of Silver Nanocluster.

Structural transformation of metal nanoclusters (NCs) is of great ongoing interest regarding their synthesis, stability, and reactivity. Although sporadic examples of cluster transformations have been reported, neither the underlying transformation mechanism nor the intermediates are unambiguous. Herein, we have synthesized a flexible 54-nuclei silver cluster (Ag54) by combining soft (tBuC≡C-) and hard (nPrCOO-) ligands. The existence of weakly coordinated nPrCOO- enhances the reactivity of Ag54, thus facilitating the dicarboxylic acid to induce structural transformation. X-ray structural analyses reveal that Ag54 transforms to Ag28 cluster-based 2D networks (Ag28a and Ag28b) induced by H2suc (succinic acid) and H2glu (glutaric acid), whereas with H2pda (2,2'-(1,2-phenylene)diacetic acid), a discrete Ag28 cluster (Ag28c) is isolated. The key intermediate Ag17 that emerges during the self-dissociation of Ag54 was isolated by using cryogenic recrystallization and characterized by X-ray crystallography. The "tandem transformation" mechanism for the structure evolution from Ag54 to Ag28a is established by time-dependent electrospray ionization mass spectrometry (ESI-MS) and UV-vis spectroscopy. In addition, the catalytic activity in the 4-nitrophenol reduction follows the sequence Ag28c > Ag28b > Ag28a > Ag54 due to more bare silver sites on the surface of the Ag28 cluster unit. Our findings not only open new avenues to the synthesis of silver NCs but also shed light on a better understanding of the structural transformation mechanism from one cluster to another or cluster-based metal-organic networks induced by dicarboxylates.

Concurrent tandem catalysis enabled by nanomechanical motion in heteroleptic four-component dual-catalyst machinery.

When the basic ligand 3 was added to the heteroleptic three-component slider-on-deck [Ag3(1)(2)]3+ (sliding frequency k298 = 57 kHz), it operated as a moderate brake pad (k298 = 45 kHz). Due to motion in the resulting four-component slider-on-deck [Ag3(1)(2)(3)]3+, both ligand 3 and silver(I) were continuously exposed and became catalytically active in a concurrent tandem Michael addition/hydroalkoxylation.

Creation of Well-Defined Pd Surface Sites on Single Crystal Pd33Ag67: From Ensembles to Single Atoms

The composition and distribution of Pd atoms on the surface were controlled by thermal treatments following sputtering of the surface of PdAg single crystal of composition Pd33Ag67 at 100 K. The Pd distribution at the (111) surface was varied from small ensembles to single atoms by thermal annealing between 400 and 820 K. On Pd ensembles, D2 dissociates readily, populating the surface with two types of atomic D/H. D2 (H2) desorbs around 295 K (β-state) from pure Pd sites, while it desorbs from bimetallic or pure silver sites desorbs around 185–230 K (γ-state). In contrast, single Pd sites did not dissociate D2 or H2 under the conditions used herein. In the annealing process rapid segregation of Pd from the topmost surface into the near subsurface occurs with annealing within minutes, and a subsequent, much slower diffusion into the bulk occurs on the time scale of hours. Moreover, subsurface Pd can be employed for fine adjustment of the chemical bonding of adsorbates to these surfaces. This study establishes a method for tuning the compositional and configurational surface properties of well-defined substitutional bimetallic bulk alloys.

Oxygen Vacancy and Metallic Silver Site Coinjection Associates Photocatalytic CO2 Reduction upon Mesoporous NH2–TiO2 Nanoparticles Assembly

Solar‐driven CO2 conversion is a promising approach to tackle the issues of increasing greenhouse gases and energy shortage. Herein, a defective amine/silver species‐modified mesoporous TiO2 (NH2–TiO2−x–Ag) nanoparticle assembly for photocatalytic CO2 reduction is reported. In particular, simultaneous oxygen vacancy incorporation and silver species anchoring in the formation of NH2–TiO2 derived from amine‐modified protonated titanate during polyol‐mediated solvothermal treatment are achieved. Indeed, the NH2–TiO2−x–Ag with different amounts of Ag species can enhance photocatalytic CO2 reduction into CH4 and CO. The NH2–TiO2−x–Ag‐0.05 sample has the highest CH4 and CO yields with rates of 6.11 and 0.91 μmol g−1 h−1, respectively, which are about 10.7 and 7 times higher than that of pristine NH2–TiO2. These findings demonstrate that the synergic impact of oxygen vacancies and metallic silver sites embedded into NH2–TiO2 can prevent poor light harvesting, fast recombination of photogenerated electrons and holes, and inadequate surface‐active sites.

Using silver exchange to achieve high uptake and selectivity for propylene/propane separation in zeolite Y

Adsorptive separation of propylene and propane, an important step of polypropylene production, is more energy-efficient than distillation. However, the challenge lies in the design of an adsorbent which exhibits both high selectivity and uptake. Herein, we hypothesise that enhancing the propylene affinity of the adsorption sites while keeping a suitable pore size can address this challenge. To do so, we performed silver exchange of a commercial zeolite Y, thereby making the adsorbent design easily scalable. We characterised the adsorbent using analytical, spectroscopic and imaging tools, tested its equilibrium and dynamic sorption properties using volumetric and gravimetric techniques and compared its performance to those of state-of-the-art adsorbents as well as other silver-functionalised adsorbents. The silver-exchanged zeolite Y (Ag-Y) exhibited one of the best selectivity vs uptake performances reported so far. Ag-Y also displayed fast adsorption kinetics and reversible propylene sorption, making it a promising new benchmark for propylene/propane separation. Synchrotron-based pair distribution function analyses identified the silver cations’ location which confirmed that the silver sites are easily accessible to the adsorbates. This aspect can, in part, explain the propylene/propane separation performance observed. The overall design strategy proposed here to enhance sorption site affinity and maintain pore size could be extended to other adsorbents and support the deployment of adsorption technology for propylene/propane separation.

A new salt-inclusion compound, |Ag4Br|@[B7O12], with a novel type of the porous double-layered borate anion and strong anharmonicity of the “guest” sublattice

A new triclinic layered borate, |Ag4Br|@[B7O12], has been prepared by glass crystallization and slow cooling stoichiometric melts in evacuated silica ampoules. The structure is based upon a layered borate anion 7:∞2 [(4: 2Δ + 2 T) + (3: 2Δ + T)] with an architecture yet not observed among inorganic borates. The layers consist of two parts comprised of tri- and tetraborate groups; it is ∼7 Å thick and oriented parallel to (001). The interlayer space is filled by the cationic [Ag4Br]3+sublattice exhibiting disorder and anharmonicity at the silver sites. The new compound was characterized by thermal analysis, high-temperature powder X-ray diffraction, vibrational and UV–Vis–NIR spectroscopy, as well as DFT calculations. For the triclinic unit cell, the eigenvalues of the thermal expansion tensor and the orientation of the thermal expansion tensor relative to the crystallographic axes are determined. The thermal expansion of the new borate bromide is strongly anisotropic, being marginal in the plane of the B–O layers (α11 = 8.2 (1), α22 = 4.71 (3) × 10−6 °С−1) while quite large in the normal direction (α33 = 38.2 (3) × 10−6).

Isolable acetylene complexes of copper and silver.

Copper and silver play important roles in acetylene transformations but isolable molecules with acetylene bonded to Cu(i) and Ag(i) ions are scarce. This report describes the stabilization of π-acetylene complexes of such metal ions supported by fluorinated and non-fluorinated, pyrazole-based chelators. These Cu(i) and Ag(i) complexes were formed readily in solutions under an atmosphere of excess acetylene and the appropriate ligand supported metal precursor, and could be isolated as crystalline solids, enabling complete characterization using multiple tools including X-ray crystallography. Molecules that display κ2-or κ3-ligand coordination modes and trigonal planar or tetrahedral metal centers have been observed. Different trends in coordination shifts of the acetylenic carbon resonance were revealed by 13C NMR spectroscopy for the Cu(i) and Ag(i) complexes. The reduction in acetylene Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> C due to metal ion coordination is relatively large for copper adducts. Computational tools were also used to quantitatively understand in detail the bonding situation in these species. It is found that the interaction between the transition metal fragment and the acetylene ligand is significantly stronger in the copper complexes, which is consistent with the experimental findings. The CC distance of these copper and silver acetylene complexes resulting from routine X-ray models suffers due to incomplete deconvolution of thermal smearing and anisotropy of the electron density in acetylene, and is shorter than expected. A method to estimate the CC distance of these metal complexes based on their experimental CC is also presented.

Exploring the Effects of a Doping Silver Atom on Anionic Gold Clusters' Reactivity with O2.

Reactivities of AgAun-1- (n = 3-10) with O2 at a low temperature were studied using an instrument combining a magnetron sputter cluster source, a microflow reactor, and a time-of-flight mass spectrometer. Their reaction products as well as size-dependent kinetic rates were nearly identical to those of corresponding Aun- (n = 3-10). Previous experiments showed that the Ag atom in AgAun-1- (n = 3-10) was fully or partially enclosed by the gold atoms. We studied the adsorption of O2 on these reported structures using the B3LYP theory with relatively large basis sets. The theoretical results indicate that the adsorption sites as well as the adsorption energies of O2 on AgAun-1- (n = 3-10) are nearly identical to those on the corresponding Aun- (n = 3-10). The O2 adsorption on a series of proposed isomers of AgAun-1- (denoted as Aun-1Ag-), in which the silver atom was on the protruding site, was explored using the same theoretical methods. The O2 tends to bond with the protruding Ag atoms, and the binding energies are apparently higher than those on the corresponding Aun- and AgAun-1-. The adsorption and activation of O2 on Aun-, AgAun-1-, and Aun-1Ag- were correlated with their global electron detachment energies (VDEs) as well as the element types of the adsorption sites. Generally, low VDE values and silver sites facilitate the O2 adsorption, and these two factors separately dominate in various cluster species. The revealed effects of a doping silver atom in small gold clusters are helpful to understand the role of the residual silver components in many nano gold catalysts.

New Ideas for Understanding the Structure and Magnetism in AgF2 : Prediction of Ferroelasticity.

In the search for new high‐temperature superconductors, it has been proposed that there are strong similarities between the fluoroargentate AgF2 and the cuprate La2CuO4. We explored the origin of the possible layered structure of AgF2 by studying its parent high‐symmetry phase and comparing these results with those of a seemingly analogous cuprate, CuF2. Our findings first stress the large differences between CuF2 and AgF2. Indeed, the parent structure of AgF2 is found to be cubic, naturally devoid of any layering, even though Ag2+ ions occupy trigonal sites that, nevertheless, allow the existence of a Jahn‐Teller effect. The observed Pbca orthorhombic phase is found when the system is cooperatively distorted by a local E⊗e trigonal Jahn‐Teller effect around the silver sites that creates both geometrical and magnetic layering. While the distortion implies that two Ag2+−F− bonds increase their distance by 15 % and become softer, our simulations indicate that covalent bonding and interlayer electron hopping is strong, unlike the situation in cuprate superconductors, and that, in fact, exfoliation of individual planes might be a harder task than previously suggested. As a salient feature, these results prove that the actual magnetic structure in AgF2 is a direct consequence of vibronic contributions involved in the Jahn‐Teller effect. Finally, our findings show that, due to the multiple minima intrinsic to the Jahn‐Teller energy surface, the system is ferroelastic, a property that is strongly coupled to magnetism in this argentate.

Local Silver Site Temperature Critically Reflected Partial and Complete Photooxidation of Ethanol Using Ag–TiO2 as Revealed by Extended X-ray Absorption Fine Structure Debye–Waller Factor

The critical factors in choosing the reaction pathway for photocatalysis are often unclear. In this study, for a typical Ag–TiO2 photocatalyst, the control factors of partial and complete oxidation of ethanol were investigated using kinetics, UV–visible and emission spectroscopy, and silver K-edge extended X-ray absorption fine structure. Low concentrations of O2-derived intermediate species that were not detected by curve-fitting analysis could be monitored under the photocatalytic conditions based on the local temperature of Ag sites provided by the Debye–Waller factor and the correlated Debye model. The site temperature monitoring was extended to Ag nanoparticles growing from 0.5 to 3.6 nm under photocatalytic reaction conditions. The Ag site temperature reached 404 K under reductive conditions to dehydrogenate ethanol into acetaldehyde, whereas it was 363–368 K under oxidative conditions owing to O2-derived species forming CO2, CH4, and H2O to suppress localized surface plasmon resonance. Under UV light, partial ethanol oxidation to acetaldehyde and O2 activation for complete oxidation to CO2 and H2O proceeded over TiO2. However, under visible light, the C–C bond cleavage to CO2 and CH4 and complete oxidation to CO2 and H2O combined with the O2-derived species transferred from the TiO2 surface proceeded over Ag0 nanoparticles.

Structure-Activity Relationships between the State of Silver on Different Supports and Their I2 and CH3I Adsorption Properties.

In this study, the performances of silver-impregnated adsorbents prepared from different host supports (SBA-15, alumina, ceria, and faujasite Y zeolite) and calcined or not at 500 °C (1 h) were compared for the capture of I2 and CH3I. By keeping the silver content rather similar (about 15–17 wt %) among the sorbents, it was possible to assess the effect of silver dispersion and speciation on the adsorption capacities measured for both adsorbates. In a first part, several characterization techniques (XRD, DRS-UV-Vis, TEM, etc.) were used to probe the state of silver in the calcined and non-calcined materials. It was found that the characteristics of silver species are strongly influenced by the thermal treatment, the presence or absence of exchange sites, and the stability of the supports. Silver agglomeration was enhanced after calcination at 500 °C especially for supports bearing no exchange sites (SBA-15) or no ordered pores (alumina and ceria). Then, the adsorption performances of the studied silver sorbents were discussed in relation with their physicochemical characteristics. After-test characterizations were useful to assess the proportion of silver species that have reacted with CH3I and I2 to yield AgI precipitates. Depending on the adsorbate, different trends were obtained. I2 adsorption/reaction with silver sites was found to be quantitative (I/Ag ≈1), whatever the silver speciation and dispersion on the support. By contrast, a high proportion of cationic silver species was found essential to increase CH3I adsorption (I/Ag about 0.6–0.7 against 0.2–0.3 for Ag agglomerated species).

Threefold Collaborative Stabilization of Ag14‐Nanorods by Hydrophobic Ti16‐Oxo Clusters and Alkynes: Designable Assembly and Solid‐State Optical‐Limiting Application

AbstractAg nanoclusters have received increasing attention due to their atomically precise and diverse structures and intriguing optical properties. Nevertheless, the inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time, Ag clusters are collaboratively protected by hydrophobic Ti‐oxo clusters and alkyne ligands. Initially, a pyramidal Ag5 cluster terminated with tBuC≡C− and CH3CN was inserted into the cavity of a Ti8‐oxo nanoring to form Ag5@Ti8. To overcome the instability of acetonitrile‐terminated silver site, such two Ag5@Ti8 clusters could sandwich an Ag4 unit to form Ag14‐nanorod@Ti16‐oxo‐nanoring (Ag14@Ti16), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti‐O shell, and terminal alkyne ligands) Ag14@Ti16 exhibits superhydrophobicity and excellent ambient stability, endowing it with solid‐state optical limiting characteristics.

Threefold Collaborative Stabilization of Ag14 -Nanorods by Hydrophobic Ti16 -Oxo Clusters and Alkynes: Designable Assembly and Solid-State Optical-Limiting Application.

Ag nanoclusters have received increasing attention due to their atomically precise and diverse structures and intriguing optical properties. Nevertheless, the inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time, Ag clusters are collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands. Initially, a pyramidal Ag5 cluster terminated with t BuC≡C- and CH3 CN was inserted into the cavity of a Ti8 -oxo nanoring to form Ag5 @Ti8 . To overcome the instability of acetonitrile-terminated silver site, such two Ag5 @Ti8 clusters could sandwich an Ag4 unit to form Ag14 -nanorod@Ti16 -oxo-nanoring (Ag14 @Ti16 ), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti-O shell, and terminal alkyne ligands) Ag14 @Ti16 exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties.

Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface-capping-agent displacement is challenging. Herein, [Ag14 (SPh(CF3 )2 )12 (PPh3 )4 (DMF)4 ] (Ag14 -DMF; DMF=N,N-dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed-ligands strategy. Owing to the high surface reactivity of Ag14 -DMF, the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation of the optical properties of Ag14 by reversible "on-off" DMF ligation was realized. When chiral amines were introduced to as-prepared products, all eight surface ligands were replaced by amines and the racemic Ag14 clusters were converted to optically pure homochiral Ag14 clusters as evidenced by circular dichroism (CD) activity and single-crystal X-ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

AbstractSurface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping‐agent displacement is challenging. Herein, [Ag14(SPh(CF3)2)12(PPh3)4(DMF)4] (Ag14‐DMF; DMF=N,N‐dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed‐ligands strategy. Owing to the high surface reactivity of Ag14‐DMF, the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation of the optical properties of Ag14 by reversible “on‐off” DMF ligation was realized. When chiral amines were introduced to as‐prepared products, all eight surface ligands were replaced by amines and the racemic Ag14 clusters were converted to optically pure homochiral Ag14 clusters as evidenced by circular dichroism (CD) activity and single‐crystal X‐ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.