Atomically Precise Nanochemistry

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Cover Title Page Copyright Page Contents List of Contributors Preface Chapter 1 Introduction to Atomically Precise Nanochemistry 1.1 Why Atomically Precise Nanochemistry? 1.1.1 Motivations from Nanoscience Research 1.1.2 Motivations from Inorganic Chemistry Research 1.1.3 Motivations from Gas Phase Cluster Research 1.1.4 Motivations from Other Areas 1.2 Types of Nanoclusters Covered in This Book 1.2.1 Atomically Precise Metal Nanoclusters (Au, Ag, Cu, Ni, Rh) 1.2.2 Endohedral Fullerenes and Graphene Nanoribbons 1.2.3 Zintl Clusters 1.2.4 Metal-Oxo Nanoclusters 1.3 Some Fundamental Aspects 1.3.1 Synthesis and Crystallization 1.3.2 Structural and Bonding Patterns 1.3.3 Transition from Nonmetallic to Metallic State: Emergence of Plasmon 1.3.4 Transition from Metal Complexes to the Cluster State: Emergence of Core 1.3.5 Doping and Alloying 1.3.6 Redox and Magnetism 1.3.7 Energy Gap Engineering 1.3.8 Assembly of Atomically Precise Nanoclusters 1.4 Some Applications 1.4.1 Chemical and Biological Sensing 1.4.2 Biomedical Imaging, Drug Delivery, and Therapy 1.4.3 Antibacteria 1.4.4 Solar Energy Conversion 1.4.5 Catalysis 1.5 Concluding Remarks Acknowledgment References Chapter 2 Total Synthesis of Thiolate-Protected Noble Metal Nanoclusters 2.1 Introduction 2.2 Size Engineering of Metal Nanoclusters 2.2.1 Size Engineering by Reduction-Growth Strategy 2.2.2 Size Engineering by Size Conversion Strategy 2.3 Composition Engineering of Metal Nanoclusters 2.3.1 Metal Composition Engineering 2.3.2 Ligand Composition Engineering 2.4 Structure Engineering of Metal Nanoclusters 2.4.1 Pseudo-Isomerization 2.4.2 Isomerization 2.5 Top-Down Etching Reaction of Metal Nanoclusters 2.6 Conclusion and Outlooks Contributions References Chapter 3 Thiolated Gold Nanoclusters with Well-Defined Compositions and Structures 3.1 Introduction 3.2 Synthesis, Purification, and Characterization of Gold Nanoclusters 3.2.1 Synthesis 3.2.1.1 Synthesis Strategy 3.2.1.2 Gold Salt (Complex) Reduction Method 3.2.1.3 Ligand Induction Method 3.2.1.4 Anti-Galvanic Reaction Method 3.2.2 Isolation and Purification 3.2.3 Characterization 3.3 Structures of Gold Nanoclusters 3.3.1 Kernel Structures of Aun(SR)m 3.3.2 Kernels Based on Tetrahedral Au4 Units 3.3.2.1 Kernels in fcc Structure 3.3.2.2 Kernels Arranged in hcp and bcc Fashions 3.3.2.3 Kernels in Mirror Symmetry and Dual-Packing (fcc and non-fcc) 3.3.2.4 Kernels Based on Icosahedral Au13 Unit 3.3.2.5 Kernels with Multiple Shells 3.3.3 Protecting Surface Motifs of Aun(SR)m Clusters 3.3.3.1 Staple-like Aux(SR)x+1 (x = 1, 2, 3, 4, 8) motifs 3.3.3.2 Ring-like Aux(SR)x (x = 4, 5, 6, 8) Motifs 3.3.3.3 Giant Au20S3(SR)18 and Au23S4(SR)18 Staple Motifs 3.3.3.4 Homo-Kernel Hetero-Staples 3.4 Properties and Applications 3.4.1 Properties 3.4.1.1 Optical Absorption 3.4.1.2 Photoluminescence 3.4.1.3 Chirality 3.4.1.4 Magnetism 3.4.2 Applications 3.4.2.1 Sensing 3.4.2.2 Biological Labeling and Biomedicine 3.4.2.3 Catalysis 3.5 Conclusion and Future Perspectives Acknowledgments References Chapter 4 Structural Design of Thiolate-Protected Gold Nanoclusters 4.1 Introduction 4.2 Structural Design Based on “Divide and Protect” Rule 4.2.1 A Brief Introduction of the Idea 4.2.2 Atomic Structure of Au68(SH)32 4.2.3 Atomic Structure of Au68(SH)34 4.3 Structural Design via Redistributing the “Staple” Motifs on the Known Au Core Structures 4.3.1 A Brief Introduction of the Idea 4.3.2 Atomic Structure of Au22(SH)17 - 4.3.3 Atomic Structures of Au27(SH)20-, Au32(SR)21-, Au34(SR)23-, and Au36(SR)25- 4.4 Structural Design via Structural Evolution 4.4.1 A Brief Introduction of the Idea 4.4.2 Atomic Structures of Au60(SR)36, Au68(SR)40, and Au76(SR)44 4.4.3 Atomic Structure of Au58(SR)30 4.5 Structural Design via Grand Unified Model 4.5.1 A Brief Introduction of the Idea 4.5.2 Atomic Structures of Hollow Au36(SR)12 and Au42(SR)14 4.5.3 Atomic Structures of Au28(SR)20 4.6 Conclusion and Perspectives Acknowledgment References Chapter 5 Electrocatalysis on Atomically Precise Metal Nanoclusters 5.1 Introduction 5.1.1 Materials Design Strategy for Electrocatalysis 5.1.2 Atomically Precise Metal Nanoclusters as Electrocatalysts 5.2 Electrochemistry of Atomically Precise Metal Nanoclusters 5.2.1 Size-Dependent Voltammetry 5.2.2 Metal-Doped Gold Nanoclusters 5.2.3 Metal-Doped Silver Nanoclusters 5.3 Electrocatalytic Water Splitting on Atomically Precise Metal Nanoclusters 5.3.1 Hydrogen Evolution Reaction: Core Engineering 5.3.2 Hydrogen Evolution Reaction: Shell Engineering 5.3.3 Hydrogen Evolution Reaction on Ag Nanoclusters 5.3.4 Oxygen Evolution Reaction 5.4 Electrocatalytic Conversion of CO2 on Atomically Precise Metal Nanoclusters 5.4.1 Mechanistic Investigation of CO2RR on Au Nanoclusters 5.4.2 Identification of CO2RR Active Sites 5.4.3 CO2RR on Cu Nanoclusters 5.4.4 Syngas Production on Formulated Metal Nanoclusters 5.5 Conclusions and Outlook Acknowledgments References Chapter 6 Atomically Precise Metal Nanoclusters as Electrocatalysts: From Experiment to Computational Insights 6.1 Introduction 6.2 Factors Affecting the Activity and Selectivity of NCs Electrocatalysis 6.2.1 Size Effect 6.2.2 Shape Effect 6.2.3 Ligands Effect 6.2.3.1 Different –R Groups in Thiolate Ligands 6.2.3.2 Different Types of Ligands 6.2.3.3 Ligand-on and -off Effect 6.2.4 Charge State Effect 6.2.5 Doping and Alloying Effect 6.3 Important Electrocatalytic Applications 6.3.1 Electrocatalytic Water Splitting 6.3.1.1 Water Electrolysis Process 6.3.1.2 Cathodic Water Reduction–HER 6.3.1.3 Anodic Water Oxidation–OER 6.3.2 Oxygen Reduction Reaction (ORR) 6.3.3 Electrochemical CO2 Reduction Reaction (CO2RR) 6.4 Conclusion and Perspectives Acknowledgments References Chapter 7 Ag Nanoclusters: Synthesis, Structure, and Properties 7.1 Introduction 7.2 Synthetic Methods 7.2.1 One-Pot Synthesis 7.2.2 Ligand Exchange 7.2.3 Chemical Etching 7.2.4 Seeded Growth Method 7.3 Structure of Ag NCs 7.3.1 Based on Icosahedral Units’ Assembly 7.3.2 Based on Ag14 Units’ Assembly 7.3.3 Other Special Ag NCs 7.4 Properties of Ag NCs 7.4.1 Chirality of Ag NCs 7.4.2 Photoluminescence of Ag NCs 7.4.3 Catalytic Properties of Ag NCs 7.5 Conclusion and Perspectives Acknowledgment References Chapter 8 Atomically Precise Copper Nanoclusters: Syntheses, Structures, and Properties 8.1 Introduction 8.2 Syntheses of Copper NCs 8.2.1 Direct Synthesis 8.2.2 Indirect Synthesis: Nanocluster-to-Nanocluster Transformation 8.3 Structures of Copper NCs 8.3.1 Superatom-like Copper NCs without Hydrides 8.3.2 Superatom-like Copper NCs with Hydrides 8.3.3 Copper(I) Hydride NCs 8.3.3.1 Determination of Hydrides 8.3.3.2 Copper(I) Hydride NCs Determined by Single-Crystal Neutron Diffraction 8.3.3.3 Copper(I) Hydride NCs Determined by Single-Crystal X-ray Diffraction 8.4 Properties 8.4.1 Photoluminescence of Copper NCs 8.4.1.1 Aggregation-Induced Emission 8.4.1.2 Circularly Polarized Luminescence (CPL) 8.4.2 Catalytic Properties of Copper NCs 8.4.2.1 Reduction of CO2 8.4.2.2 “Click” Reaction 8.4.2.3 Hydrogenation 8.4.2.4 Carbonylation Reactions 8.4.3 Other Properties 8.4.3.1 Hydrogen Storage 8.4.3.2 Electronic Devices 8.5 Summary Comparison with Gold and Silver NCs 8.6 Conclusion and Perspectives References Chapter 9 Atomically Precise Nanoclusters of Iron, Cobalt, and Nickel: Why Are They So Rare? 9.1 Introduction 9.2 General Considerations 9.3 Synthesis of Ni APNCs 9.4 Synthesis of Co APNCs 9.5 Attempted Synthesis of Fe APNCs 9.6 Conclusions and Outlook Acknowledgments References Chapter 10 Atomically Precise Heterometallic Rhodium Nanoclusters Stabilized by Carbonyl Ligands 10.1 Introduction 10.1.1 Metal Carbonyl Clusters: A Brief Historical Overview 10.1.2 State of the Art on Rhodium Carbonyl Clusters 10.2 Synthesis of Heterometallic Rhodium Carbonyl Nanoclusters 10.2.1 Synthesis of the [Rh12E(CO)27]n. Family of Nanoclusters 10.2.2 Growth of Rhodium Heterometallic Nanoclusters 10.2.2.1 Rh-Ge Nanoclusters 10.2.2.2 Rh-Sn Nanoclusters 10.2.2.3 Rh-Sb Nanoclusters 10.2.2.4 Rh-Bi Nanoclusters 10.3 Electron-Reservoir Behavior of Heterometallic Rhodium Nanoclusters 10.4 Conclusions and Perspectives Acknowledgments References Chapter 11 Endohedral Fullerenes: Atomically Precise Doping Inside Nano Carbon Cages 11.1 Introduction 11.2 Synthesis of Endohedral Metallofullerenes 11.3 Fullerene Structures Tuned by Endohedral Doping 11.3.1 Geometry of Empty and Endohedral Fullerene Cage Structures 11.3.2 Conventional Endohedral Metallofullerenes 11.3.2.1 Mono-Metallofullerens 11.3.2.2 Di-Metallofullerenes 11.3.3 Clusterfullerenes 11.3.3.1 Nitride Clusterfullerenes 11.3.3.2 Carbide Clusterfullerenes 11.3.3.3 Oxide and Sulfide Clusterfullerenes 11.3.3.4 Carbonitride and Cyanide Clusterfullerenes 11.4 Properties Tuned by Endohedral Doping 11.4.1 Spectroscopic Properties 11.4.1.1 NMR Spectroscopy 11.4.1.2 Absorption Spectroscopy 11.4.1.3 Vibrational Spectroscopy 11.4.2 Electrochemical Properties 11.4.2.1 Conventional Endohedral Metallofullerenes 11.4.2.2 Clusterfullerenes 11.4.3 Magnetic Properties 11.4.3.1 Dimetallofullerenes 11.4.3.2 Clusterfullerenes 11.5 Chemical Reactivity Tune by Endohedral Doping 11.5.1 Impact of Endohedral Doping on the Reactivity of Fullerene Cages 11.5.2 Chemical Reactivity of Endohedral Fullerenes Altered by Atomically Endohedral Doping 11.6 Conclusions and Perspectives References Chapter 12 On-Surface Synthesis of Polyacenes and Narrow Band-Gap Graphene Nanoribbons 12.1 Introduction 12.1.1 Nanocarbon Materials 12.1.2 Graphene Nanoribbons 12.2 Bottom-Up Synthesis of Graphene Nanoribbons 12.3 On-Surface Synthesis of Narrow Bandgap Armchair-Type Graphene Nanoribbons 12.4 On-Surface Synthesis of Polyacenes as Partial Structure of Zigzag-Type Graphene Nanoribbons 12.5 Conclusion and Perspectives Acknowledgments References Chapter 13 A Branch of Zintl Chemistry: Metal Clusters of Group 15 Elements 13.1 Introduction 13.1.1 Homoatomic Group 15 Clusters 13.1.2 Bonding Concepts 13.1.3 Aromaticity in Zintl Chemistry 13.2 Complex Coordination Modes in Arsenic Clusters 13.3 Antimony Clusters with Aromaticity and Anti-Aromaticity 13.4 Recent Advances in Bismuth-Containing Compounds 13.5 Ternary Clusters Containing Group 15 Elements 13.6 Conclusion and Perspectives References Chapter 14 Exploration of Controllable Synthesis and Structural Diversity of Titanium─Oxo Clusters 14.1 Introduction 14.2 Coordination Delayed Hydrolysis Strategy 14.2.1 Solvothermal Synthesis 14.2.2 Aqueous Sol-Gel Synthesis 14.2.3 Ionothermal Synthesis 14.2.4 Solid-State-Like Synthesis 14.3 Ti-O Core Diversity 14.3.1 Dense Structures 14.3.2 Wheel-Shaped Structures 14.3.3 Sphere-Shaped Structures 14.3.4 Multicluster Structures 14.4 Ligand Diversity 14.4.1 Carboxylate Ligands 14.4.2 Phosphonate Ligands 14.4.3 Polyphenolic Ligands 14.4.4 Sulfate Ligands 14.4.5 Nitrogen Heterocyclic Ligands 14.5 Metal-Doping Diversity 14.5.1 Transition Metal Doping 14.5.2 Rare Earth Metal Doping 14.6 Structural Influence on Properties and Applications 14.7 Conclusion and Perspectives Acknowledgment References Chapter 15 Atom-Precise Cluster-Assembled Materials: Requirement and Progresses 15.1 Introduction 15.2 Prospect of Cluster-Assembling Process and Their Classification 15.2.1 Nanocluster Assembly in Crystal Lattice through Surface Ligand Interaction 15.2.2 Nanocluster Assembly through Metal–Metal Bonds 15.2.3 Nanocluster Assembly through Linkers 15.2.3.1 One-Dimensional Nanocluster Assembly 15.2.3.2 Two-Dimensional Nanocluster Assembly 15.2.3.3 Three-Dimensional Nanocluster Assembly 15.2.4 Nanocluster Assembly through Aggregation 15.3 Conclusions and Outlook Notes Acknowledgments References Chapter 16 Coinage Metal Cluster-Assembled Materials 16.1 Introduction 16.2 Structures of Metal Cluster-Assembled Materials 16.2.1 Silver Cluster-Assembled Materials (SCAMs) 16.2.1.1 Simple Ion Linker 16.2.1.2 POMs Linker 16.2.1.3 Organic Linker 16.2.2 Gold Cluster-Assembled Materials (GCAMs) 16.2.3 Copper Cluster-Assembled Materials (CCAMs) 16.3 Applications 16.3.1 Ratiometric Luminescent Temperature Sensing 16.3.2 Luminescent Sensing and Identifying O2 and VOCs 16.3.3 Catalytic Properties 16.3.4 Anti-Superbacteria 16.4 Conclusion Acknowledgments References Index EULA 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 nanoparti-cles but also to provide new opportunities for applications such as catalysis, optics, and biomedi-cine. Given the breadth of the book, De-en and I decided to invite a number of experts who are working on various types of atomically precise nanoclusters. We thank all the experts for their warm support of the book and timely completion of the chapters. Due to space limitations, we must apologize to some colleagues for missing their excellent work that could not be included in this book.This book comprises 16 chapters. Chapter 1 provides an introduction to atomically precise nano-chemistry. Chapters 2 to 10 cover atomically precise metal nanoclusters, such as Au, Ag, Cu, Ni, Rh, and the doped/alloyed nanoclusters, as well as the electrocatalytic application in CO2 reduc-tion and water splitting. Endohedral metallofullerenes, graphene nanoribbons, Zintl clusters, and Ti-oxo nanoclusters are discussed in Chapters 11 to 14, respectively. Finally, Chapters 15 and 16 are devoted to the assembly of nanoclusters (such as Au, Ag, and Cu), including the crystalline assembly and the use of nanoclusters as nodes for constructing special types of metal-organic frameworks, as well as the sensing and other applications. The atomic-level control in the synthe-sis, the new types of structures, and the physical/chemical properties of nanoclusters are illus-trated in various chapters.This book contains not only experimental contributions but also theoretical insights into the atomic and electronic structures, as well as the catalytic mechanisms. We expect this book to be suitable for graduate and undergraduate students, researchers, and industry practitioners. Atomically Precise Nanochemistry 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. "This book summarizes recent progress in the development of atomically precise nanochemistry and will be an important state-of-the-art reference for the broad communities of nanoscience and cluster science, ranging from chemistry, physics, biology, materials science, to engineering. The book is divided into six parts, each covering a different type of nanocluster: metal nanoclusters (Au, Ag, Pd, Pt, Al, alloys),, semiconductor nanoclusters (CdSe, ZnS, InAs), metal-oxo systems (Mo-O, Ti-O, W-O), large-sized organometallic nano-architectures, carbon clusters (fullerenes, small nanoribbons), and supramolecular architectures. For each type of nanocluster, chapters cover experimental aspects - synthesis, structure and applications - and theory - electronic structure, geometry, and bonding ? with a focus on structure-property relationships throughout the book."-- Provided by publisher