List of Contributors xiii Preface xvii 1 Introduction to Atomically Precise Nanochemistry 1 Rongchao Jin 1.1 Why Atomically Precise Nanochemistry? 1 1.1.1 Motivations from Nanoscience Research 1 1.1.2 Motivations from Inorganic Chemistry Research 5 1.1.3 Motivations from Gas Phase Cluster Research 6 1.1.4 Motivations from Other Areas 6 1.2 Types of Nanoclusters Covered in This Book 7 1.2.1 Atomically Precise Metal Nanoclusters (Au, Ag, Cu, Ni, Rh) 8 1.2.2 Endohedral Fullerenes and Graphene Nanoribbons 10 1.2.3 Zintl Clusters 10 1.2.4 Metal- Oxo Nanoclusters 11 1.3 Some Fundamental Aspects 12 1.3.1 Synthesis and Crystallization 12 1.3.2 Structural and Bonding Patterns 16 1.3.3 Transition from Nonmetallic to Metallic State: Emergence of Plasmon 25 1.3.4 Transition from Metal Complexes to the Cluster State: Emergence of Core 29 1.3.5 Doping and Alloying 32 1.3.6 Redox and Magnetism 33 1.3.7 Energy Gap Engineering 39 1.3.8 Assembly of Atomically Precise Nanoclusters 40 1.4 Some Applications 42 1.4.1 Chemical and Biological Sensing 43 1.4.2 Biomedical Imaging, Drug Delivery, and Therapy 44 1.4.3 Antibacteria 45 1.4.4 Solar Energy Conversion 45 1.4.5 Catalysis 45 1.5 Concluding Remarks 49 Acknowledgment 49 References 49 2 Total Synthesis of Thiolate- Protected Noble Metal Nanoclusters 57 Qiaofeng Yao, Yitao Cao, Tiankai Chen, and Jianping Xie 2.1 Introduction 57 2.2 Size Engineering of Metal Nanoclusters 58 2.2.1 Size Engineering by Reduction- Growth Strategy 58 2.2.2 Size Engineering by Size Conversion Strategy 62 2.3 Composition Engineering of Metal Nanoclusters 64 2.3.1 Metal Composition Engineering 64 2.3.2 Ligand Composition Engineering 70 2.4 Structure Engineering of Metal Nanoclusters 73 2.4.1 Pseudo- Isomerization 75 2.4.2 Isomerization 75 2.5 Top- Down Etching Reaction of Metal Nanoclusters 78 2.6 Conclusion and Outlooks 80 Contributions 83 References 83 3 Thiolated Gold Nanoclusters with Well- Defined Compositions and Structures 87 Wanmiao Gu and Zhikun Wu 3.1 Introduction 87 3.2 Synthesis, Purification, and Characterization of Gold Nanoclusters 88 3.2.1 Synthesis 88 3.2.1.1 Synthesis Strategy 89 3.2.1.2 Gold Salt (Complex) Reduction Method 89 3.2.1.3 Ligand Induction Method 91 3.2.1.4 Anti- Galvanic Reaction Method 91 3.2.2 Isolation and Purification 92 3.2.3 Characterization 94 3.3 Structures of Gold Nanoclusters 95 3.3.1 Kernel Structures of Au n (SR) m 96 3.3.2 Kernels Based on Tetrahedral Au 4 Units 96 3.3.2.1 Kernels in fcc Structure 99 3.3.2.2 Kernels Arranged in hcp and bcc Fashions 99 3.3.2.3 Kernels in Mirror Symmetry and Dual- Packing (fcc and non- fcc) 101 3.3.2.4 Kernels Based on Icosahedral Au 13 Unit 102 3.3.2.5 Kernels with Multiple Shells 105 3.3.3 Protecting Surface Motifs of Au n (SR) m Clusters 111 3.3.3.1 Staple- Like Au X (sr) X+1 (x = 1, 2, 3, 4, 8) Motifs 111 3.3.3.2 Ring- Like Au X (sr) X (x = 4, 5, 6, 8) Motifs 111 3.3.3.3 Giant Au 20 S 3 (SR) 18 and Au 23 S 4 (SR) 18 Staple Motifs 112 3.3.3.4 Homo- Kernel Hetero- Staples 112 3.4 Properties and Applications 115 3.4.1 Properties 115 3.4.1.1 Optical Absorption 116 3.4.1.2 Photoluminescence 119 3.4.1.3 Chirality 123 3.4.1.4 Magnetism 124 3.4.2 Applications 125 3.4.2.1 Sensing 125 3.4.2.2 Biological Labeling and Biomedicine 127 3.4.2.3 Catalysis 127 3.5 Conclusion and Future Perspectives 130 Acknowledgments 131 References 131 4 Structural Design of Thiolate- Protected Gold Nanoclusters 141 Pengye Liu, Wenhua Han, and Wen Wu Xu 4.1 Introduction 141 4.2 Structural Design Based on “Divide and Protect” Rule 142 4.2.1 A Brief Introduction of the Idea 142 4.2.2 Atomic Structure of Au 68 (SH) 32 142 4.2.3 Atomic Structure of Au 68 (SH) 34 142 4.3 Structural Design via Redistributing the “Staple” Motifs on the Known Au Core Structures 144 4.3.1 A Brief Introduction of the Idea 144 4.3.2− Atomic Structure of Au 22 (SH) 17 145 4.3.3 Atomic Structures of Au 27 (SH) − 20 , Au 32 (SR) − 21 , Au 34 (SR) − 23 , and Au 36 (SR) 25 − 146 4.4 Structural Design via Structural Evolution 149 4.4.1 A Brief Introduction of the Idea 149 4.4.2 Atomic Structures of Au 60 (SR) 36 , Au 68 (SR) 40 , and Au 76 (SR) 44 150 4.4.3 Atomic Structure of Au 58 (SR) 30 152 4.5 Structural Design via Grand Unified Model 153 4.5.1 A Brief Introduction of the Idea 153 4.5.2 Atomic Structures of Hollow Au 36 (SR) 12 and Au 42 (SR) 14 154 4.5.3 Atomic Structures of Au 28 (SR) 20 155 4.6 Conclusion and Perspectives 155 Acknowledgment 156 References 156 5 Electrocatalysis on Atomically Precise Metal Nanoclusters 161 Hoeun Seong, Woojun Choi, Yongsung Jo, and Dongil Lee 5.1 Introduction 161 5.1.1 Materials Design Strategy for Electrocatalysis 161 5.1.2 Atomically Precise Metal Nanoclusters as Electrocatalysts 163 5.2 Electrochemistry of Atomically Precise Metal Nanoclusters 164 5.2.1 Size- Dependent Voltammetry 164 5.2.2 Metal- Doped Gold Nanoclusters 166 5.2.3 Metal- Doped Silver Nanoclusters 169 5.3 Electrocatalytic Water Splitting on Atomically Precise Metal Nanoclusters 170 5.3.1 Hydrogen Evolution Reaction: Core Engineering 170 5.3.2 Hydrogen Evolution Reaction: Shell Engineering 172 5.3.3 Hydrogen Evolution Reaction on Ag Nanoclusters 173 5.3.4 Oxygen Evolution Reaction 176 5.4 Electrocatalytic Conversion of CO 2 on Atomically Precise Metal Nanoclusters 178 5.4.1 Mechanistic Investigation of CO 2 RR on Au Nanoclusters 179 5.4.2 Identification of CO 2 RR Active Sites 181 5.4.3 CO 2 RR on Cu Nanoclusters 183 5.4.4 Syngas Production on Formulated Metal Nanoclusters 185 5.5 Conclusions and Outlook 187 Acknowledgments 188 References 188 6 Atomically Precise Metal Nanoclusters as Electrocatalysts: From Experiment to Computational Insights 195 Fang Sun, Qing Tang, and De- en Jiang 6.1 Introduction 195 6.2 Factors Affecting the Activity and Selectivity of NCs Electrocatalysis 196 6.2.1 Size Effect 196 6.2.2 Shape Effect 198 6.2.3 Ligands Effect 199 6.2.3.1 Different –R Groups in Thiolate Ligands 199 6.2.3.2 Different Types of Ligands 199 6.2.3.3 Ligand- on and - off Effect 200 6.2.4 Charge State Effect 201 6.2.5 Doping and Alloying Effect 202 6.3 Important Electrocatalytic Applications 205 6.3.1 Electrocatalytic Water Splitting 205 6.3.1.1 Water Electrolysis Process 205 6.3.1.2 Cathodic Water Reduction–HER 206 6.3.1.3 Anodic Water Oxidation–OER 208 6.3.2 Oxygen Reduction Reaction (ORR) 210 6.3.3 Electrochemical CO 2 Reduction Reaction (CO 2 RR) 213 6.4 Conclusion and Perspectives 219 Acknowledgments 220 References 220 7 Ag Nanoclusters: Synthesis, Structure, and Properties 227 Manman Zhou and Manzhou Zhu 7.1 Introduction 227 7.2 Synthetic Methods 228 7.2.1 One- Pot Synthesis 228 7.2.2 Ligand Exchange 228 7.2.3 Chemical Etching 229 7.2.4 Seeded Growth Method 229 7.3 Structure of Ag NCs 229 7.3.1 Based on Icosahedral Units’ Assembly 231 7.3.2 Based on Ag 14 Units’ Assembly 235 7.3.3 Other Special Ag NCs 241 7.4 Properties of Ag NCs 245 7.4.1 Chirality of Ag NCs 245 7.4.2 Photoluminescence of Ag NCs 247 7.4.3 Catalytic Properties of Ag NCs 250 7.5 Conclusion and Perspectives 250 Acknowledgment 251 References 251 8 Atomically Precise Copper Nanoclusters: Syntheses, Structures, and Properties 257 Chunwei Dong, Saidkhodzha Nematulloev, Peng Yuan, and Osman M. Bakr 8.1 Introduction 257 8.2 Syntheses of Copper NCs 258 8.2.1 Direct Synthesis 258 8.2.2 Indirect Synthesis: Nanocluster- to- Nanocluster Transformation 260 8.3 Structures of Copper NCs 261 8.3.1 Superatom- like Copper NCs without Hydrides 261 8.3.2 Superatom- like Copper NCs with Hydrides 263 8.3.3 Copper(I) Hydride NCs 265 8.3.3.1 Determination of Hydrides 265 8.3.3.2 Copper(I) Hydride NCs Determined by Single- Crystal Neutron Diffraction 265 8.3.3.3 Copper(I) Hydride NCs Determined by Single- Crystal X- ray Diffraction 268 8.4 Properties 270 8.4.1 Photoluminescence of Copper NCs 270 8.4.1.1 Aggregation- Induced Emission 271 8.4.1.2 Circularly Polarized Luminescence (CPL) 273 8.4.2 Catalytic Properties of Copper NCs 273 8.4.2.1 Reduction of CO 2 273 8.4.2.2 “Click” Reaction 276 8.4.2.3 Hydrogenation 276 8.4.2.4 Carbonylation Reactions 276 8.4.3 Other Properties 276 8.4.3.1 Hydrogen Storage 276 8.4.3.2 Electronic Devices 277 8.5 Summary Comparison with Gold and Silver NCs 277 8.6 Conclusion and Perspectives 278 References 279 9 Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel: Why Are They So Rare? 285 Trevor W. Hayton 9.1 Introduction 285 9.2 General Considerations 287 9.3 Synthesis of Ni APNCs 288 9.4 Synthesis of Co APNCs 294 9.5 Attempted Synthesis of Fe APNCs 297 9.6 Conclusions and Outlook 299 Acknowledgments 300 References 300 10 Atomically Precise Heterometallic Rhodium Nanoclusters Stabilized by Carbonyl Ligands 309 Guido Bussoli, Cristiana Cesari, Cristina Femoni, Maria C. Iapalucci, Silvia Ruggieri, and Stefano Zacchini 10.1 Introduction 309 10.1.1 Metal Carbonyl Clusters: A Brief Historical Overview 309 10.1.2 State of the Art on Rhodium Carbonyl Clusters 310 10.2 Synthesis of Heterometallic Rhodium Carbonyl Nanoclusters 311 10.2.1 Synthesis of the [Rh12 E(CO)27 ] n− Family of Nanoclusters 311 10.2.2 Growth of Rhodium Heterometallic Nanoclusters 314 10.2.2.1 Rh─Ge Nanoclusters 314 10.2.2.2 Rh─Sn Nanoclusters 316 10.2.2.3 Rh─Sb Nanoclusters 316 10.2.2.4 Rh─Bi Nanoclusters 319 10.3 Electron- Reservoir Behavior of Heterometallic Rhodium Nanoclusters 319 10.4 Conclusions and Perspectives 322 Acknowledgments 324 References 324 11 Endohedral Fullerenes: Atomically Precise Doping Inside Nano Carbon Cages 331 Yang- Rong Yao, Jiawei Qiu, Lihao Zheng, Hongjie Jiang, Yunpeng Xia, and Ning Chen 11.1 Introduction 331 11.2 Synthesis of Endohedral Metallofullerenes 332 11.3 Fullerene Structures Tuned by Endohedral Doping 334 11.3.1 Geometry of Empty and Endohedral Fullerene Cage Structures 334 11.3.2 Conventional Endohedral Metallofullerenes 336 11.3.2.1 Mono- Metallofullerens 336 11.3.2.2 Di- Metallofullerenes 337 11.3.3 Clusterfullerenes 339 11.3.3.1 Nitride Clusterfullerenes 339 11.3.3.2 Carbide Clusterfullerenes 339 11.3.3.3 Oxide and Sulfide Clusterfullerenes 341 11.3.3.4 Carbonitride and Cyanide Clusterfullerenes 341 11.4 Properties Tuned by Endohedral Doping 342 11.4.1 Spectroscopic Properties 342 11.4.1.1 NMR Spectroscopy 343 11.4.1.2 Absorption Spectroscopy 344 11.4.1.3 Vibrational Spectroscopy 347 11.4.2 Electrochemical Properties 349 11.4.2.1 Conventional Endohedral Metallofullerenes 349 11.4.2.2 Clusterfullerenes 351 11.4.3 Magnetic Properties 353 11.4.3.1 Dimetallofullerenes 353 11.4.3.2 Clusterfullerenes 354 11.5 Chemical Reactivity Tune by Endohedral Doping 358 11.5.1 Impact of Endohedral Doping on the Reactivity of Fullerene Cages 358 11.5.2 Chemical Reactivity of Endohedral Fullerenes Altered by Atomically Endohedral Doping 360 11.6 Conclusions and Perspectives 362 References 362 12 On- Surface Synthesis of Polyacenes and Narrow Band- Gap Graphene Nanoribbons 373 Hironobu Hayashi and Hiroko Yamada 12.1 Introduction 373 12.1.1 Nanocarbon Materials 374 12.1.2 Graphene Nanoribbons 374 12.2 Bottom- Up Synthesis of Graphene Nanoribbons 375 12.3 On- Surface Synthesis of Narrow Bandgap Armchair- Type Graphene Nanoribbons 378 12.4 On- Surface Synthesis of Polyacenes as Partial Structure of Zigzag- Type Graphene Nanoribbons 382 12.5 Conclusion and Perspectives 390 Acknowledgments 390 References 390 13 A Branch of Zintl Chemistry: Metal Clusters of Group 15 Elements 395 Yu-He Xu, Nikolay V. Tkachenko, Alvaro Muñoz-Castro, Alexander I. Boldyrev, and Zhong- Ming Sun 13.1 Introduction 395 13.1.1 Homoatomic Group 15 Clusters 395 13.1.2 Bonding Concepts 396 13.1.3 Aromaticity in Zintl Chemistry 397 13.2 Complex Coordination Modes in Arsenic Clusters 399 13.3 Antimony Clusters with Aromaticity and Anti- Aromaticity 401 13.4 Recent Advances in Bismuth- Containing Compounds 408 13.5 Ternary Clusters Containing Group 15 Elements 411 13.6 Conclusion and Perspectives 414 References 415 14 Exploration of Controllable Synthesis and Structural Diversity of Titanium─Oxo Clusters 423 Mei- Yan Gao, Lei Zhang, and Jian Zhang 14.1 Introduction 423 14.2 Coordination Delayed Hydrolysis Strategy 425 14.2.1 Solvothermal Synthesis 426 14.2.2 Aqueous Sol- Gel Synthesis 426 14.2.3 Ionothermal Synthesis 427 14.2.4 Solid- State- Like Synthesis 427 14.3 Ti─O Core Diversity 427 14.3.1 Dense Structures 431 14.3.2 Wheel- Shaped Structures 431 14.3.3 Sphere- Shaped Structures 431 14.3.4 Multicluster Structures 432 14.4 Ligand Diversity 432 14.4.1 Carboxylate Ligands 433 14.4.2 Phosphonate Ligands 433 14.4.3 Polyphenolic Ligands 435 14.4.4 Sulfate Ligands 436 14.4.5 Nitrogen Heterocyclic Ligands 437 14.5 Metal- Doping Diversity 438 14.5.1 Transition Metal Doping 439 14.5.2 Rare Earth Metal Doping 440 14.6 Structural Influence on Properties and Applications 441 14.7 Conclusion and Perspectives 445 Acknowledgment 446 References 446 15 Atom- Precise Cluster- Assembled Materials: Requirement and Progresses 453 Sourav Biswas, Panpan Sun, Xia Xin, Sukhendu Mandal, and Di Sun 15.1 Introduction 453 15.2 Prospect of Cluster- Assembling Process and Their Classification 454 15.2.1 Nanocluster Assembly in Crystal Lattice through Surface Ligand Interaction 455 15.2.2 Nanocluster Assembly through Metal–Metal Bonds 456 15.2.3 Nanocluster Assembly through Linkers 461 15.2.3.1 One- Dimensional Nanocluster Assembly 463 15.2.3.2 Two- Dimensional Nanocluster Assembly 465 15.2.3.3 Three- Dimensional Nanocluster Assembly 469 15.2.4 Nanocluster Assembly through Aggregation 470 15.3 Conclusions and Outlook 474 Notes 474 Acknowledgments 475 References 475 16 Coinage Metal Cluster- Assembled Materials 479 Zhao- Yang Wang and Shuang- Quan Zang 16.1 Introduction 479 16.2 Structures of Metal Cluster- Assembled Materials 480 16.2.1 Silver Cluster- Assembled Materials (SCAMs) 480 16.2.1.1 Simple Ion Linker 480 16.2.1.2 POMs Linker 482 16.2.1.3 Organic Linker 482 16.2.2 Gold Cluster- Assembled Materials (GCAMs) 491 16.2.3 Copper Cluster- Assembled Materials (CCAMs) 492 16.3 Applications 493 16.3.1 Ratiometric Luminescent Temperature Sensing 494 16.3.2 Luminescent Sensing and Identifying O2 and VOCs 495 16.3.3 Catalytic Properties 495 16.3.4 Anti- Superbacteria 498 16.4 Conclusion 499 Acknowledgments 499 References 499 Index 503

Explore recent progress and developments in atomically precise nanochemistry Chemists have long been motivated to create atomically precise nanoclusters, not only for addressing some fundamental issues that were not possible to tackle with imprecise nanoparticles, but also to provide new opportunities for applications such as catalysis, optics, and biomedicine. In Atomically Precise Nanochemistry, a team of distinguished researchers delivers a state-of-the-art reference for researchers and industry professionals working in the fields of nanoscience and cluster science, in disciplines ranging from chemistry to physics, biology, materials science, and engineering. A variety of different nanoclusters are covered, including metal nanoclusters, semiconductor nanoclusters, metal-oxo systems, large-sized organometallic nano-architectures, carbon clusters, and supramolecular architectures. The book contains not only experimental contributions, but also theoretical insights into the atomic and electronic structures, as well as the catalytic mechanisms. The authors explore synthesis, structure, geometry, bonding, and applications of each type of nanocluster. Perfect for researchers working in nanoscience, nanotechnology, and materials chemistry, Atomically Precise Nanochemistry will also benefit industry professionals in these sectors seeking a practical and up-to-date resource.