Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters

Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters | 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 Research Article Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters Juefei Dai, Chuanhua Shi, Zhixun Zhang, Yan Nong, Chenchen Feng, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6046680/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 18 You are reading this latest preprint version Abstract In the realm of nanomaterials science, the precise and controllable synthesis of nanoclusters remains a formidable challenge. This study focuses on the synthesis of silver sulfide nanoclusters via the halide ion template method, with an in - depth exploration of the underlying synthesis mechanism. By meticulously regulating halogen ion concentration, reaction solvent, and other reaction parameters, a diverse array of nanoclusters with distinct structures has been successfully fabricated and characterized at the atomic - precision level using X-ray single crystal diffraction. The results clearly demonstrate that halogen ion concentration exerts a profound influence on the structural characteristics of the clusters. Different halogen ions can trigger the formation of disparate nucleation sites and structures, and the choice of solvent also plays a crucial role in determining the structural properties of the clusters. halogen ions nanoclusters single-crystal structures silver sulfide Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction The precise and controllable synthesis of nanoclusters is a central issue in the field of nanomaterials science[ 1 ]. Nanoclusters, with their unique quantum size effect and surface atom - dependent properties, hold great promise for applications in various fields such as catalysis[ 2 – 7 ], optoelectronics[ 8 – 14 ], and biosensing[ 15 , 16 ]. Silver sulfide (Ag 2 S) nanoclusters have attracted significant attention in recent years due to their narrow band gap[ 17 ], excellent photothermal stability[ 18 ], and favorable biocompatibility[ 19 , 20 ]. However, traditional synthesis methods, including solvothermal solvothermal[ 21 – 23 ] and chemical reduction techniques[ 24 – 29 ], often encounter difficulties in precisely controlling the size, morphology, and crystallinity of the clusters. This leads to poor reproducibility of their properties, limiting their practical applications The template method offers a novel approach for the controlled synthesis of nanoclusters[ 30 – 35 ]. By introducing specific anions as structure - directing agents, it can dynamically coordinate with metal precursors, thereby regulating the nucleation kinetics and crystal growth paths. This enables precise control over the cluster size, crystal phase, and surface structure. Currently, several types of template anions are utilized in the synthesis of silver nanoclusters: (1) Oxygenate-containing ions: e.g., SO₄²⁻, NO₃⁻, PO₄³⁻, binding to silver ions through strong electrostatic interactions. Although they can regulate the nucleation kinetics and crystal growth paths via ligand interactions, their single coordination mode makes it challenging to construct complex structures [ 36 – 44 ]; (2) Organic anions: e.g., sulfonates, they can modulate the surface properties of the clusters through the diversity of their functional groups. However, they suffer from poor thermal stability and are prone to introduce impurities during the synthesis process[ 45 , 46 ]; (3) Polymetallic oxonate anions: they have structural tunability but require harsh synthesis conditions and high costs, which restricts their widespread use [ 47 – 53 ]; (4) Halogen ions: Cl⁻, Br⁻, I⁻, show unique potential as inorganic templates[ 18 , 54 – 60 ]. The template effect of halide ions can be attributed to their variable ionic radii (Cl − < Br − < I − ) and strong coordination tendency with silver ions[ 61 ]. On the one hand, halogen ions can regulate the nucleation sites of clusters through size effects. For instance, the smaller radius of Cl⁻ tends to promote the formation of dense nuclear structures, while the larger radius of I⁻ induces the generation of open backbones[ 55 , 62 ]. This property allows for the targeted design of clusters with specific sizes and porosities, making them promising for a wide range of applications[ 63 , 64 ]. On the other hand, the dynamic reversibility of the halogen-silver coordination bond facilitates structural self-correction during the synthesis process, enhancing the crystallinity of the products. Additionally, the introduction of halogen ions can modulate the energy band structure of Ag 2 S. Nevertheless, this strategy also faces challenges. Halogen ions are prone to desorption at high temperatures or in acidic environments. Competitive coordination between different halogen ions may trigger phase separation, and halogen residues can affect the surface chemistry of the clusters, necessitating the development of efficient post - purification methods. This study aims to comprehensively investigate the mechanism of the halogen ion template method in the controlled synthesis of Ag₂S nanoclusters. A systematic analysis of the effects of ion radius, concentration, and coordination environment on the cluster structure is conducted, with the goal of providing a theoretical basis and technological breakthroughs for the precise preparation of high performance nanoclusters. 2. Results and Discussion 2.1 Synthesis In this work, the synthesis of the products was precisely controlled by modulating the solvent, halogen ion concentration, reaction temperature, and reaction time. The detailed synthesis process is provided in the Supporting Information (SI). Halide ions exhibit strong coordination with Ag⁺ and possess a relatively large solubility product (Ksp), which competes with S²⁻/SR. This competition indicates that the concentration of halide ions has a significant impact on the structure of the products. The experimental approach involved using AgSC 6 H 4 t Bu as the precursor, and tetramethyl halogen ammonia salt and tetrabutyl halogen ammonia salt as the templates. By carefully adjusting the template concentration, reaction solvent, and reaction time, the structural configuration of the products was precisely regulated. The addition of a small amount of water during the reaction process was a crucial factor in obtaining crystals suitable for single - crystal diffraction testing. This is likely because water can participate in the coordination environment, affecting the growth kinetics of the nanoclusters and facilitating the formation of well - ordered crystal structures. 2.2 Analysis of cluster structure In a previous study, we successfully synthesized Br@Ag 36 nanoclusters using Br − as a template and characterized their crystal structures, determining them to be highly symmetric windmill structures[65]. In this work, when the dosage of tetramethyl bromide was increased compared to the previous experiment, clusters with completely different structural features were obtained. Single-crystal structure analysis of the new product revealed a molecular formula of [Br 2 @Ag 28 S (SC 6 H 4 t Bu) 36 Br 2 ] 4− . As depicted in Fig. 1, the symmetry of the complete structure decreases, adopting a beanpole shape. The increase in Br − concentration results in an increase in the amount of Br in the product. Two Br − are encapsulated in the center of the cluster in the shape of a bean horn. These Br⁻ ions form weak coordination bonds with Ag, with the Br - Ag bond length ranging from 2.886 (5) Å to 3.046 (8) Å, and an average bond length of 2.95. 4(8) Å. In addition, other two Br atoms coordinated with Ag + as surface ligands, symmetrically distributed near the ends of the bean-like structure, with a bond length of 2.576(5) Å. When tetramethyl ammonium chloride was used instead of tetramethyl bromide, the expected Cl@Ag 36 was successfully obtained (Fig. 2). Single-crystal structure analysis showed that the crystal structure of Cl@Ag 36 is similar to that of the previously reported Br@Ag 36 . The whole structure resembles a windmill with two centers crossing and overlapping, exhibiting triple symmetry. Cl − is located in the middle of the hollow cage at the center of the structure. The central cage can be described as Cl@(Ag 3 SR 3 ) 2 @Ag 12 SR 6 , with two Ag 3 SR 3 cross-symmetrically distributed at the top and bottom of the cage, and Ag 12 SR 6 joining the two Ag 3 SR 3 into a sealed cage at the waist of the cage. The cage is surrounded by six “SR - Ag - SR” units, similar to “staple” structures, which bind the waist of the cage. Due to the presence of the SR - Ag - SR structural units, the whole structure is chiral and exhibits C 3 symmetry. However, the structure has chiral flip properties, so there is no enantiomer and its space group is non-chiral. When the solvent was changed from acetonitrile to a mixture of acetonitrile and acetone (acetonitrile: acetone = 2:1) while continuing to use tetramethylammonium bromide / tetramethylammonium chloride as templating agents, Br 2 @Ag 28 and Cl 2 @Ag 28 were obtained. As shown in Fig. 3, their structures are similar to Br 2 @Ag 28 Br 2 in the form of a bowtie, with the molecular formulas Br 2 @Ag 28 (SC 6 H 4 t Bu) 30 and Cl 2 @Ag 28 (SC 6 H 4 t Bu) 30 . Unlike the previous clusters, these two clusters are molecularly neutral. The clusters also contain two Br − /Cl − as templates due to the high concentration of halogen ions, and Br − forms a weak coordination bond with Ag + with an average bond length of 2.961(3) Å. The change in solvent likely affects the solvation of the reactants and the intermediate species, altering the reaction kinetics and the way halogen ions coordinate with Ag⁺. This, in turn, leads to a change in the cluster structure from the original windmill or beanpole shape to the bowtie shape. After replacing tetramethyl ammonium chloride with tetrabutyl ammonium chloride, two new clusters with different structures were obtained at different Cl − concentrations. When the Cl − concentration was low, light yellow transparent crystals were obtained. Single - crystal structure testing revealed a molecular formula of (NBu 4 ) 2 [Ag 23 (SC 6 H 4 t Bu) 24 ]. As shown in Fig. 4, due to the low Cl⁻ concentration and the absence of Cl ions as templating agents, the Ag₂₂ structure has a flattened cloverleaf shape. . When the Cl − concentration is elevated, Cl − enters the cluster structure acting as a template with the molecular formula (NBu 4 ) 2 [Cl@Ag 23 (SC 6 H 4 t Bu) 24 ]. As shown in Fig. 5, the entire structure is chiral and exhibits C 3 symmetry due to the formation of a “staple” structure “SR-Ag-SR”. The structure can be further described as Cl@Ag 5 @Ag 18 (SR) 24 , where the Cl ion is located in a trigonal bipyramid formed by five Ag atoms, which is surrounded by Ag 6 (SR) 8 with C 3 helically symmetrically distributed, forming a topology similar to that of a trilobal junction. Since the enantiomers occur in pairs in each single-cell structure, the entire cluster is racemic. The 23 Ag atoms in the structure can be categorized as µ 2 , µ 3 , and µ 4 based on their coordination mode with SR. Using the same strategy, when tetrabutylammonium bromide was used to introduce the anionic template, crystals were obtained. However, due to the inherent disorder of Ag - S clusters, the single - crystal structure could not be successfully resolved. In the case of the I − ion as a template, although crystals meeting the test conditions were obtained by precisely controlling the reaction conditions, the crystal structure could not be resolved due to its extremely high symmetry and disordered nature. These results clearly demonstrate that the concentration of halogen ions have a significant impact on the structure of the clusters. Lower concentrations of halogen ions may not be able to participate in the construction of the core structure of the clusters, resulting in clusters with simpler shapes, such as the flat cloverleaf shape of Ag 22 at low concentrations of Cl − . Higher halogen ion concentrations, on the other hand, participate in the structure formation of the clusters, influencing their symmetry and overall morphology. Different halogen ions induce different cluster structures due to differences in ionic radius and coordination ability. The change of solvent also has a non - negligible effect on the cluster structure. The use of a mixed solvent of acetonitrile and acetone changes the cluster structure from the original windmill or beanpole shape to the bowtie shape, which is likely due to the change in the physicochemical properties of the reaction system, such as polarity and dielectric constant, affecting the coordination process of halogen ions with Ag⁺ and the growth kinetics of the clusters. 3. Summary In this study, we conducted an in - depth analysis of the mechanism of the halogen ion template method in the controllable synthesis of silver sulfide nanoclusters. By systematically varying the halogen ion species, concentration, and reaction solvent, a variety of nanoclusters with unique structural features were successfully prepared, and their single - crystal structures were analyzed in detail. We clarified the key influence of halogen ion concentration on the cluster structure. Different halogen ions can induce the formation of diverse clusters, such as windmill - like, bean - horn - like, bowtie - like, and clusters with a trilobal junction topology under different conditions. Meanwhile, we found that the change of solvent also significantly affects the cluster structure. These research results reveal the intrinsic relationship between the ionic radius, concentration, coordination environment, and cluster structure. This provides an important basis for a deeper understanding of the formation mechanism of nanoclusters, enriching the knowledge system of nanocluster synthesis chemistry at the theoretical level. Moreover, it offers practical theoretical guidance and technical references for the precise preparation of high - performance nanoclusters in practical applications, which is expected to promote the further development and wide application of nanoclusters in the fields of catalysis, optoelectronics, and biosensing. Declarations Acknowledgements We are grateful for the financial support from Shenzhen Science and Technology Program (KQTD20221101093605019), Medical-Engineering Interdisciplinary Research Foundation of Shenzhen University (2023YG001), Shenzhen Science and Technology Innovation Commission (JCYJ20220531101202005), and Shenzhen Key Laboratory of Nano-Biosensing Technology (ZDSYS20210112161400001). The authors also thank the Instrumental Analysis Center of Shenzhen University for the technical assistance. Data availability All data needed to support the conclusions in the paper are presented in the manuscript and the Electronic Supplementary Material. Additional data related to this paper may be requested from the corresponding author upon request. Declaration of competing interest The authors declare no competing financial interest. Author contribution statement Juefei Dai, Chuahua Shi and Zhixun Zhang are contributed equally to this work. 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Supplementary Files SIHalideIonTemplatedAtomicPrecisionSynthesisandStructuralModulationofSilverSulfideNanoclustersSZU.docx TableofContents.docx Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 21 Feb, 2025 Reviewers agreed at journal 20 Feb, 2025 Reviews received at journal 20 Feb, 2025 Reviews received at journal 20 Feb, 2025 Reviews received at journal 20 Feb, 2025 Reviewers agreed at journal 20 Feb, 2025 Reviewers agreed at journal 20 Feb, 2025 Reviewers agreed at journal 20 Feb, 2025 Reviews received at journal 19 Feb, 2025 Reviews received at journal 19 Feb, 2025 Reviewers agreed at journal 19 Feb, 2025 Reviews received at journal 19 Feb, 2025 Reviewers agreed at journal 19 Feb, 2025 Reviewers agreed at journal 19 Feb, 2025 Reviewers invited by journal 19 Feb, 2025 Editor assigned by journal 19 Feb, 2025 Submission checks completed at journal 19 Feb, 2025 First submitted to journal 17 Feb, 2025 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. 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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-6046680","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":418815870,"identity":"f0161924-5d35-4ac3-aadb-f5473d11863e","order_by":0,"name":"Juefei Dai","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Juefei","middleName":"","lastName":"Dai","suffix":""},{"id":418815871,"identity":"07e96168-a9a9-4256-9be9-fa7423aaac5a","order_by":1,"name":"Chuanhua Shi","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Chuanhua","middleName":"","lastName":"Shi","suffix":""},{"id":418815872,"identity":"3c2525ca-3209-4f1b-8276-9912f0ae802a","order_by":2,"name":"Zhixun Zhang","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Zhixun","middleName":"","lastName":"Zhang","suffix":""},{"id":418815874,"identity":"b6c10c50-6fb3-4da0-a232-91b8e3042ae1","order_by":3,"name":"Yan Nong","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Yan","middleName":"","lastName":"Nong","suffix":""},{"id":418815875,"identity":"3081d6b8-2910-41c2-a7ca-6b0716f1ff60","order_by":4,"name":"Chenchen Feng","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Chenchen","middleName":"","lastName":"Feng","suffix":""},{"id":418815876,"identity":"16fe3ff4-566e-446a-b1e4-8ae7b44f798c","order_by":5,"name":"Xianyong Yu","email":"","orcid":"","institution":"Hunan University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Xianyong","middleName":"","lastName":"Yu","suffix":""},{"id":418815878,"identity":"0903c77c-4443-4f29-a0ab-d991e5005b2b","order_by":6,"name":"Chao Yang","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Chao","middleName":"","lastName":"Yang","suffix":""},{"id":418815879,"identity":"37a8f2e6-26a7-4ecb-b303-1a7fab97bde1","order_by":7,"name":"Xueji Zhang","email":"","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":false,"prefix":"","firstName":"Xueji","middleName":"","lastName":"Zhang","suffix":""},{"id":418815881,"identity":"785bd981-6b94-4588-add1-7b361af3d7f9","order_by":8,"name":"Huayan Yang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA8UlEQVRIiWNgGAWjYJACZih1AEIfIF4LWwLJWngMiNNicPzs4deFbXaJ/bN7Pn/82cYgx3cjgfFzAT4tZ/LSrGe2JSfOuHN2m4RkG4Ox5I0EZukZ+LQcyDEz5m1jTmy4kbuNwbCNIXHDjQQ2Zh58Ws6/AWmpT5x/I+fxh8Q2hnrCWm7kGD/mbTsMNDyHQeJgG0OCASEtkjfemDHznDtuvPFGmplkwzkJw5lnHjZL49PCdz7H+DNPWbXsvBvJjz/+KLOR5zuefPAzPi0KBxjYJIC0YwOED2IzNuDRwMAg38DA/AFI2+NVNQpGwSgYBSMbAACf71HaREvYvQAAAABJRU5ErkJggg==","orcid":"","institution":"Technology，Shenzhen University Medical School， Shenzhen University，Shenzhen","correspondingAuthor":true,"prefix":"","firstName":"Huayan","middleName":"","lastName":"Yang","suffix":""}],"badges":[],"createdAt":"2025-02-17 09:53:45","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6046680/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6046680/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":76830481,"identity":"b3e20c85-8466-4886-8baa-0f78a764167b","added_by":"auto","created_at":"2025-02-21 08:22:10","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":657341,"visible":true,"origin":"","legend":"\u003cp\u003eThe crystal structure of\u003cstrong\u003e \u003c/strong\u003e[Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003eS (SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e36\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e4-\u003c/sup\u003e. Color codes: green, Ag; olive-green; yellow, S; purple, Br; grey stick, C\u003c/p\u003e","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/0982d2060a06046830e31e83.png"},{"id":76831418,"identity":"3354b669-8615-4429-bd14-9d0901e2a6ce","added_by":"auto","created_at":"2025-02-21 08:30:10","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1075400,"visible":true,"origin":"","legend":"\u003cp\u003eThe structure of the [Cl@Ag\u003csub\u003e36\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e36\u003c/sub\u003e]\u003csup\u003e- \u003c/sup\u003ecluster. Color codes: green, Ag; olive-green, Ag; purple blue, Ag; bluish blue, Ag; yellow, S; orange, Cl\u003c/p\u003e","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/352e494954fb72c9181ba3a8.png"},{"id":76830477,"identity":"348c90b4-c656-4ae5-988a-3cf139373d5d","added_by":"auto","created_at":"2025-02-21 08:22:10","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":874735,"visible":true,"origin":"","legend":"\u003cp\u003eThe structure of the Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e30 \u003c/sub\u003eand Cl\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e30\u003c/sub\u003e. Color codes: green, Ag; yellow, S; orange, Cl; purple, Br; grey stick, C\u003c/p\u003e","description":"","filename":"Figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/d909a78ce294456a54c0b676.png"},{"id":76830487,"identity":"e9b3b884-fa81-4db4-9c19-939045f1357e","added_by":"auto","created_at":"2025-02-21 08:22:10","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":655423,"visible":true,"origin":"","legend":"\u003cp\u003eThe structure of the [Ag\u003csub\u003e23\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e24\u003c/sub\u003e]\u003csup\u003e2-\u003c/sup\u003e. Color codes: green, Ag; yellow, S; grey stick, C\u003c/p\u003e","description":"","filename":"Figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/85dfa144069760c6fe0e6922.png"},{"id":76830483,"identity":"7c85cfa1-6910-45d0-9517-434425899d4a","added_by":"auto","created_at":"2025-02-21 08:22:10","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":516203,"visible":true,"origin":"","legend":"\u003cp\u003eThe structure of [Cl@Ag\u003csub\u003e23\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e24\u003c/sub\u003e]\u003csup\u003e2-\u003c/sup\u003e. Color codes: green, Ag; blue, Ag; dark blue, Ag; yellow, S; orange, Cl\u003c/p\u003e","description":"","filename":"Figure5.png","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/dc3200d7d492f148f5e17b3c.png"},{"id":76831923,"identity":"d475d9d3-9d63-4b15-a6ec-e5e645daa048","added_by":"auto","created_at":"2025-02-21 08:38:20","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4087243,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/bde5137d-1b53-4900-9b44-887d3cc88e11.pdf"},{"id":76831422,"identity":"c0c6f87b-956a-4556-85d8-acbcea474dd8","added_by":"auto","created_at":"2025-02-21 08:30:10","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3386017,"visible":true,"origin":"","legend":"","description":"","filename":"SIHalideIonTemplatedAtomicPrecisionSynthesisandStructuralModulationofSilverSulfideNanoclustersSZU.docx","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/289bcf34bd5d5f4785d781e9.docx"},{"id":76831419,"identity":"69e80941-0423-482e-9c76-8e7911fe97f8","added_by":"auto","created_at":"2025-02-21 08:30:10","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":309908,"visible":true,"origin":"","legend":"","description":"","filename":"TableofContents.docx","url":"https://assets-eu.researchsquare.com/files/rs-6046680/v1/b79810d6ac840b2576c2429b.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe precise and controllable synthesis of nanoclusters is a central issue in the field of nanomaterials science[\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e]. Nanoclusters, with their unique quantum size effect and surface atom - dependent properties, hold great promise for applications in various fields such as catalysis[\u003cspan class=\"CitationRef\"\u003e2\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e7\u003c/span\u003e], optoelectronics[\u003cspan class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e14\u003c/span\u003e], and biosensing[\u003cspan class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e16\u003c/span\u003e]. Silver sulfide (Ag\u003csub\u003e2\u003c/sub\u003eS) nanoclusters have attracted significant attention in recent years due to their narrow band gap[\u003cspan class=\"CitationRef\"\u003e17\u003c/span\u003e], excellent photothermal stability[\u003cspan class=\"CitationRef\"\u003e18\u003c/span\u003e], and favorable biocompatibility[\u003cspan class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e20\u003c/span\u003e]. However, traditional synthesis methods, including solvothermal solvothermal[\u003cspan class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e23\u003c/span\u003e] and chemical reduction techniques[\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e29\u003c/span\u003e], often encounter difficulties in precisely controlling the size, morphology, and crystallinity of the clusters. This leads to poor reproducibility of their properties, limiting their practical applications\u003c/p\u003e\n\u003cp\u003eThe template method offers a novel approach for the controlled synthesis of nanoclusters[\u003cspan class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e35\u003c/span\u003e]. By introducing specific anions as structure - directing agents, it can dynamically coordinate with metal precursors, thereby regulating the nucleation kinetics and crystal growth paths. This enables precise control over the cluster size, crystal phase, and surface structure. Currently, several types of template anions are utilized in the synthesis of silver nanoclusters: (1) Oxygenate-containing ions: e.g., SO₄\u0026sup2;⁻, NO₃⁻, PO₄\u0026sup3;⁻, binding to silver ions through strong electrostatic interactions. Although they can regulate the nucleation kinetics and crystal growth paths via ligand interactions, their single coordination mode makes it challenging to construct complex structures [\u003cspan class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e44\u003c/span\u003e]; (2) Organic anions: e.g., sulfonates, they can modulate the surface properties of the clusters through the diversity of their functional groups. However, they suffer from poor thermal stability and are prone to introduce impurities during the synthesis process[\u003cspan class=\"CitationRef\"\u003e45\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e46\u003c/span\u003e]; (3) Polymetallic oxonate anions: they have structural tunability but require harsh synthesis conditions and high costs, which restricts their widespread use [\u003cspan class=\"CitationRef\"\u003e47\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e]; (4) Halogen ions: Cl⁻, Br⁻, I⁻, show unique potential as inorganic templates[\u003cspan class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e60\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eThe template effect of halide ions can be attributed to their variable ionic radii (Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026lt; Br\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026lt; I\u003csup\u003e\u0026minus;\u003c/sup\u003e) and strong coordination tendency with silver ions[\u003cspan class=\"CitationRef\"\u003e61\u003c/span\u003e]. On the one hand, halogen ions can regulate the nucleation sites of clusters through size effects. For instance, the smaller radius of Cl⁻ tends to promote the formation of dense nuclear structures, while the larger radius of I⁻ induces the generation of open backbones[\u003cspan class=\"CitationRef\"\u003e55\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e62\u003c/span\u003e]. This property allows for the targeted design of clusters with specific sizes and porosities, making them promising for a wide range of applications[\u003cspan class=\"CitationRef\"\u003e63\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e64\u003c/span\u003e]. On the other hand, the dynamic reversibility of the halogen-silver coordination bond facilitates structural self-correction during the synthesis process, enhancing the crystallinity of the products. Additionally, the introduction of halogen ions can modulate the energy band structure of Ag\u003csub\u003e2\u003c/sub\u003eS. Nevertheless, this strategy also faces challenges. Halogen ions are prone to desorption at high temperatures or in acidic environments. Competitive coordination between different halogen ions may trigger phase separation, and halogen residues can affect the surface chemistry of the clusters, necessitating the development of efficient post - purification methods.\u003c/p\u003e\n\u003cp\u003eThis study aims to comprehensively investigate the mechanism of the halogen ion template method in the controlled synthesis of Ag₂S nanoclusters. A systematic analysis of the effects of ion radius, concentration, and coordination environment on the cluster structure is conducted, with the goal of providing a theoretical basis and technological breakthroughs for the precise preparation of high \u0026nbsp;performance nanoclusters.\u003c/p\u003e"},{"header":"2. Results and Discussion","content":"\u003cdiv id=\"Sec3\"\u003e\n \u003ch2\u003e2.1 Synthesis\u003c/h2\u003e\n \u003cp\u003eIn this work, the synthesis of the products was precisely controlled by modulating the solvent, halogen ion concentration, reaction temperature, and reaction time. The detailed synthesis process is provided in the Supporting Information (SI). Halide ions exhibit strong coordination with Ag⁺ and possess a relatively large solubility product (Ksp), which competes with S²⁻/SR. This competition indicates that the concentration of halide ions has a significant impact on the structure of the products.\u003c/p\u003e\n \u003cp\u003eThe experimental approach involved using AgSC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu as the precursor, and tetramethyl halogen ammonia salt and tetrabutyl halogen ammonia salt as the templates. By carefully adjusting the template concentration, reaction solvent, and reaction time, the structural configuration of the products was precisely regulated. The addition of a small amount of water during the reaction process was a crucial factor in obtaining crystals suitable for single - crystal diffraction testing. This is likely because water can participate in the coordination environment, affecting the growth kinetics of the nanoclusters and facilitating the formation of well - ordered crystal structures.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\"\u003e\n \u003ch2\u003e2.2 Analysis of cluster structure\u003c/h2\u003e\n \u003cp\u003eIn a previous study, we successfully synthesized Br@Ag\u003csub\u003e36\u003c/sub\u003enanoclusters using Br\u003csup\u003e−\u003c/sup\u003e as a template and characterized their crystal structures, determining them to be highly symmetric windmill structures[65]. In this work, when the dosage of tetramethyl bromide was increased compared to the previous experiment, clusters with completely different structural features were obtained. Single-crystal structure analysis of the new product revealed a molecular formula of [Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003eS (SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e36\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e4−\u003c/sup\u003e. As depicted in Fig.\u0026nbsp;1, the symmetry of the complete structure decreases, adopting a beanpole shape. The increase in Br\u003csup\u003e−\u003c/sup\u003e concentration results in an increase in the amount of Br in the product. Two Br\u003csup\u003e−\u003c/sup\u003e are encapsulated in the center of the cluster in the shape of a bean horn. These Br⁻ ions form weak coordination bonds with Ag, with the Br - Ag bond length ranging from 2.886 (5) Å to 3.046 (8) Å, and an average bond length of 2.95. 4(8) Å. In addition, other two Br atoms coordinated with Ag\u003csup\u003e+\u003c/sup\u003e as surface ligands, symmetrically distributed near the ends of the bean-like structure, with a bond length of 2.576(5) Å.\u003c/p\u003e\n \u003cp\u003eWhen tetramethyl ammonium chloride was used instead of tetramethyl bromide, the expected Cl@Ag\u003csub\u003e36\u003c/sub\u003e was successfully obtained (Fig.\u0026nbsp;2). Single-crystal structure analysis showed that the crystal structure of Cl@Ag\u003csub\u003e36\u003c/sub\u003e is similar to that of the previously reported Br@Ag\u003csub\u003e36\u003c/sub\u003e. The whole structure resembles a windmill with two centers crossing and overlapping, exhibiting triple symmetry. Cl\u003csup\u003e−\u003c/sup\u003e is located in the middle of the hollow cage at the center of the structure. The central cage can be described as Cl@(Ag\u003csub\u003e3\u003c/sub\u003eSR\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e12\u003c/sub\u003eSR\u003csub\u003e6\u003c/sub\u003e, with two Ag\u003csub\u003e3\u003c/sub\u003eSR\u003csub\u003e3\u003c/sub\u003e cross-symmetrically distributed at the top and bottom of the cage, and Ag\u003csub\u003e12\u003c/sub\u003eSR\u003csub\u003e6\u003c/sub\u003e joining the two Ag\u003csub\u003e3\u003c/sub\u003eSR\u003csub\u003e3\u003c/sub\u003e into a sealed cage at the waist of the cage. The cage is surrounded by six “SR - Ag - SR” units, similar to “staple” structures, which bind the waist of the cage. Due to the presence of the SR - Ag - SR structural units, the whole structure is chiral and exhibits C\u003csub\u003e3\u003c/sub\u003e symmetry. However, the structure has chiral flip properties, so there is no enantiomer and its space group is non-chiral.\u003c/p\u003e\n \u003cp\u003eWhen the solvent was changed from acetonitrile to a mixture of acetonitrile and acetone (acetonitrile: acetone = 2:1) while continuing to use tetramethylammonium bromide / tetramethylammonium chloride as templating agents, Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e and Cl\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e were obtained. As shown in Fig.\u0026nbsp;3, their structures are similar to Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003e in the form of a bowtie, with the molecular formulas Br\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e (SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e30\u003c/sub\u003e and Cl\u003csub\u003e2\u003c/sub\u003e@Ag\u003csub\u003e28\u003c/sub\u003e (SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e30\u003c/sub\u003e. Unlike the previous clusters, these two clusters are molecularly neutral. The clusters also contain two Br\u003csup\u003e−\u003c/sup\u003e/Cl\u003csup\u003e−\u003c/sup\u003e as templates due to the high concentration of halogen ions, and Br\u003csup\u003e−\u003c/sup\u003e forms a weak coordination bond with Ag\u003csup\u003e+\u003c/sup\u003e with an average bond length of 2.961(3) Å. The change in solvent likely affects the solvation of the reactants and the intermediate species, altering the reaction kinetics and the way halogen ions coordinate with Ag⁺. This, in turn, leads to a change in the cluster structure from the original windmill or beanpole shape to the bowtie shape.\u003c/p\u003e\n \u003cp\u003eAfter replacing tetramethyl ammonium chloride with tetrabutyl ammonium chloride, two new clusters with different structures were obtained at different Cl\u003csup\u003e−\u003c/sup\u003e concentrations. When the Cl\u003csup\u003e−\u003c/sup\u003e concentration was low, light yellow transparent crystals were obtained. Single - crystal structure testing revealed a molecular formula of (NBu\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e[Ag\u003csub\u003e23\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e24\u003c/sub\u003e]. As shown in Fig.\u0026nbsp;4, due to the low Cl⁻ concentration and the absence of Cl ions as templating agents, the Ag₂₂ structure has a flattened cloverleaf shape. .\u003c/p\u003e\n \u003cp\u003eWhen the Cl\u003csup\u003e−\u003c/sup\u003e concentration is elevated, Cl\u003csup\u003e−\u003c/sup\u003e enters the cluster structure acting as a template with the molecular formula (NBu\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e[Cl@Ag\u003csub\u003e23\u003c/sub\u003e(SC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003et\u003c/sup\u003eBu)\u003csub\u003e24\u003c/sub\u003e]. As shown in Fig.\u0026nbsp;5, the entire structure is chiral and exhibits C\u003csub\u003e3\u003c/sub\u003e symmetry due to the formation of a “staple” structure “SR-Ag-SR”. The structure can be further described as Cl@Ag\u003csub\u003e5\u003c/sub\u003e@Ag\u003csub\u003e18\u003c/sub\u003e(SR)\u003csub\u003e24\u003c/sub\u003e, where the Cl ion is located in a trigonal bipyramid formed by five Ag atoms, which is surrounded by Ag\u003csub\u003e6\u003c/sub\u003e(SR)\u003csub\u003e8\u003c/sub\u003e with C\u003csub\u003e3\u003c/sub\u003e helically symmetrically distributed, forming a topology similar to that of a trilobal junction. Since the enantiomers occur in pairs in each single-cell structure, the entire cluster is racemic. The 23 Ag atoms in the structure can be categorized as µ\u003csub\u003e2\u003c/sub\u003e, µ\u003csub\u003e3\u003c/sub\u003e, and µ\u003csub\u003e4\u003c/sub\u003e based on their coordination mode with SR.\u003c/p\u003e\n \u003cp\u003eUsing the same strategy, when tetrabutylammonium bromide was used to introduce the anionic template, crystals were obtained. However, due to the inherent disorder of Ag - S clusters, the single - crystal structure could not be successfully resolved. In the case of the I\u003csup\u003e−\u003c/sup\u003e ion as a template, although crystals meeting the test conditions were obtained by precisely controlling the reaction conditions, the crystal structure could not be resolved due to its extremely high symmetry and disordered nature.\u003c/p\u003e\n \u003cp\u003eThese results clearly demonstrate that the concentration of halogen ions have a significant impact on the structure of the clusters. Lower concentrations of halogen ions may not be able to participate in the construction of the core structure of the clusters, resulting in clusters with simpler shapes, such as the flat cloverleaf shape of Ag\u003csub\u003e22\u003c/sub\u003e at low concentrations of Cl\u003csup\u003e−\u003c/sup\u003e. Higher halogen ion concentrations, on the other hand, participate in the structure formation of the clusters, influencing their symmetry and overall morphology. Different halogen ions induce different cluster structures due to differences in ionic radius and coordination ability. The change of solvent also has a non - negligible effect on the cluster structure. The use of a mixed solvent of acetonitrile and acetone changes the cluster structure from the original windmill or beanpole shape to the bowtie shape, which is likely due to the change in the physicochemical properties of the reaction system, such as polarity and dielectric constant, affecting the coordination process of halogen ions with Ag⁺ and the growth kinetics of the clusters.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"3. Summary","content":"\u003cp\u003eIn this study, we conducted an in - depth analysis of the mechanism of the halogen ion template method in the controllable synthesis of silver sulfide nanoclusters. By systematically varying the halogen ion species, concentration, and reaction solvent, a variety of nanoclusters with unique structural features were successfully prepared, and their single - crystal structures were analyzed in detail.\u003c/p\u003e \u003cp\u003eWe clarified the key influence of halogen ion concentration on the cluster structure. Different halogen ions can induce the formation of diverse clusters, such as windmill - like, bean - horn - like, bowtie - like, and clusters with a trilobal junction topology under different conditions. Meanwhile, we found that the change of solvent also significantly affects the cluster structure.\u003c/p\u003e \u003cp\u003eThese research results reveal the intrinsic relationship between the ionic radius, concentration, coordination environment, and cluster structure. This provides an important basis for a deeper understanding of the formation mechanism of nanoclusters, enriching the knowledge system of nanocluster synthesis chemistry at the theoretical level. Moreover, it offers practical theoretical guidance and technical references for the precise preparation of high - performance nanoclusters in practical applications, which is expected to promote the further development and wide application of nanoclusters in the fields of catalysis, optoelectronics, and biosensing.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe are grateful for the financial support from Shenzhen Science and Technology Program (KQTD20221101093605019), Medical-Engineering Interdisciplinary Research Foundation of Shenzhen University (2023YG001), Shenzhen Science and Technology Innovation Commission (JCYJ20220531101202005), and Shenzhen Key Laboratory of Nano-Biosensing Technology (ZDSYS20210112161400001). The authors also thank the Instrumental Analysis Center of Shenzhen University for the technical assistance.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data needed to support the conclusions in the paper are presented in the manuscript and the Electronic Supplementary Material. Additional data related to this paper may be requested from the corresponding author upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eJuefei Dai, Chuahua Shi and Zhixun Zhang are contributed equally to this work. Juefei Dai, Chuahua Shi and Zhixun Zhang: Conceived and carried out experiments, analyzed data and wrote the paper; Chengcheng Feng and Yan Nong: Assisted in SCXRD measurement and crystal structure refinements; Chao Yang and Xianyong Yu: Assisted data analyzed; Xueji Zhang Project administration; Huayan Yang Project administration, writing manuscript, experimental design, funding acquisition, designed the study, supervised the project, analyzed data and wrote the paper.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eJin, R., Zeng, C., Zhou, M. \u0026amp; Chen, Y. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e116\u003c/strong\u003e, 10346-10413, (2016).\u003c/li\u003e\n \u003cli\u003eDu, Y., Sheng, H., Astruc, D. \u0026amp; Zhu, M. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e120\u003c/strong\u003e, 526-622, (2019).\u003c/li\u003e\n \u003cli\u003eDeng, G.\u003cem\u003e\u0026nbsp;et al.\u003c/em\u003e \u003cem\u003eJ. Am. Chem. 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This study focuses on the synthesis of silver sulfide nanoclusters via the halide ion template method, with an in - depth exploration of the underlying synthesis mechanism. By meticulously regulating halogen ion concentration, reaction solvent, and other reaction parameters, a diverse array of nanoclusters with distinct structures has been successfully fabricated and characterized at the atomic - precision level using X-ray single crystal diffraction. The results clearly demonstrate that halogen ion concentration exerts a profound influence on the structural characteristics of the clusters. Different halogen ions can trigger the formation of disparate nucleation sites and structures, and the choice of solvent also plays a crucial role in determining the structural properties of the clusters.\u003c/p\u003e","manuscriptTitle":"Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-02-21 08:22:05","doi":"10.21203/rs.3.rs-6046680/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-02-21T07:32:03+00:00","index":"","fulltext":""},{"type":"reviewerAgreed","content":"29955953974882428261706802873039165578","date":"2025-02-21T02:06:38+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-21T00:54:33+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-21T00:38:02+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-20T14:08:35+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"84011316275506878264255107946669839401","date":"2025-02-20T10:15:02+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"295566590725093832904063098767276487344","date":"2025-02-20T09:19:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"170992442358334662950690283647915989853","date":"2025-02-20T08:27:00+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-20T03:13:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-20T02:36:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"206728662226325058012404718767975205891","date":"2025-02-20T02:22:04+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-20T01:23:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"26744184481216833021137642440885949336","date":"2025-02-20T00:57:26+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"23671414905683020741418111712835497830","date":"2025-02-19T20:04:10+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-02-19T15:15:30+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-02-19T09:37:49+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-02-19T08:22:31+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Cluster Science","date":"2025-02-17T09:50:30+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-cluster-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Journal of Cluster Science](https://www.springer.com/journal/10876) ","snPcode":"10876","submissionUrl":"https://mc.manuscriptcentral.com/jocl","title":"Journal of Cluster Science","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"d16a40d5-5c34-44fb-b670-e54ce9e6a890","owner":[],"postedDate":"February 21st, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2025-02-24T11:23:41+00:00","versionOfRecord":[],"versionCreatedAt":"2025-02-21 08:22:05","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6046680","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6046680","identity":"rs-6046680","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}