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 โDivide and Protectโ 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 โStapleโ 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 โR 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 ReductionโHER
6.3.1.3 Anodic Water OxidationโOER
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 Unitsโ Assembly
7.3.2 Based on Ag14 Unitsโ 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 โClickโ 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 TitaniumโOxo 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 MetalโMetal 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
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