Atomically Precise Metal Nanoclusters

Front cover
Half title
Title
Copyright
Contents
Contributors
Preface
Acknowledgments
Chapter 1 Atomically precise clusters of noble metals: An introduction
References
Chapter 2 Structure and chemical properties of clusters
2.1 Introduction
2.2 Chemical reactivity at the nanoscale: Beyond surface to volume ratio
2.3 Chemical reactivity at the nanoscale: A brief historical overview
2.4 Chemical properties of atomically precise metal clusters: Insights from gas phase studies
2.4.1 Geometric versus electronic stability in unprotected, gaseous phase metal clusters
2.5 Molecule-like nature of ligand-protected atomically precise noble metal clusters
2.5.1 Superatom concept for ligand-protected noble metal clusters
2.6 Chemistry of ligand-protected atomically precise noble metal clusters: A structural view
2.6.1 Substitution of ligands
2.6.2 Ligand-induced structural transformations
2.6.3 Substitution of metal atoms
2.7 Electrochemical properties of metal clusters
2.7.1 Reactions with metal ions
2.7.2 Reactions with halocarbons
2.8 Stereochemistry of ligand protected atomically precise metal clusters
2.8.1 Chirality due to the presence of chiral ligands
2.8.2 Chirality due to the chiral arrangement of achiral ligands on achiral metal core
2.8.3 Chirality due to inherently chiral metal core
2.8.4 Chirality due to encapsulation into chiral supramolecules or hosts
2.8.5 Chirality in metal clusters: structure-property correlations
2.9 Intercluster reactions
2.9.1 Reaction between Au25(PET)18 and Ag44(FTP)30
2.9.2 Reaction between Au25(FTP)18 and Ag44(FTP)30: Shell closing effects
in intercluster reactions
2.9.3 Reaction between Au25(PET)18 and Ag25(DMBT)18
2.9.4 Dynamic nature of the clusters and intercluster reactivity
2.9.5 What triggers intercluster exchange reactivity?—The role of
metal–ligand interface
2.9.6 Should the metal atoms be different for exchange reactivity: Isotope exchange between clusters
2.10 Understanding the reaction mechanisms: Where are we?
2.10.1 Mechanistic insights into intercluster reactions
2.10.2 Mechanisms of metal atom substitution reactions
2.11 Achieving atomic precision in cluster chemistry—A few examples
2.11.1 Single ligand exchange in a redox reaction
2.11.2 Site-selective substitution of metal atoms via reaction with
metal–thiolates and metal–phosphine complexes
2.11.3 Site-selective Au atom substitution in [Ag44(p-MBA)30]4−
2.12 Summary and future perspectives
References
Chapter 3 Nanocluster assembled solids
3.1 Introduction
3.2 Limitation of nanocluster solidification
3.2.1 Synthetic limitations
3.2.2 Purification
3.2.3 Stability of nanoclusters
3.3 Methods of nanocluster solidification
3.3.1 Crystallization
3.3.2 Gelation
3.4 Single crystal structure determination
3.5 Different types of nanocluster assembled solids
3.5.1 Nanocluster crystals
3.5.2 Nanocluster assembled gels
3.5.3 Nanoclusters in confined solid
3.6 Properties of nanocluster assembled solids
3.6.1 Photoluminescence
3.6.2 Conductivity
3.6.3 Magnetic property
3.6.4 Mechanical property
3.6.5 Catalytic property
3.6.6 Hypergolic property
3.7 Summary and future perspective
References
Chapter 4 Optical properties of metal clusters
4.1 Introduction
4.2 Optical absorption spectroscopy
4.3 Optical spectroscopy of archetypal clusters
4.3.1 Au25 and Ag25
4.3.2 Ag44 and analogous clusters
4.3.3 Au38, Au102, and larger clusters
4.3.4 Size evolution and metallicity
4.4 Photoluminescence of clusters
4.5 Dynamics of excited states
4.5.1 Common methods and examples
4.6 Nonlinear processes
4.6.1 Two-photon absorption and emission
4.6.2 Second-order processes
4.6.3 Third-order processes
4.6.4 Optical limiting
4.7 Computational methods and optical properties
4.8 Summary and future perspectives
References
Chapter 5 Supramolecular chemistry of nanoclusters
5.1 Introduction to supramolecular chemistry
5.2 Fullerenes
5.3 Cyclodextrins
5.4 Cucurbiturils
5.5 Crown ethers
5.6 Properties of supramolecular complexes of NCs
5.7 Applications of supramolecular complexes of NCs
5.8 Summary and future perspectives
References
Chapter 6 Nanocluster–nanoparticle
coassemblies
6.1 Introduction
6.2 Importance of colloidal assembly
6.3 NCs in colloidal assembly
6.3.1 NP–NC assembly leading to precise hierarchical structures
6.3.2 Assemblies leading to enhanced or emerging properties
6.4 NP–NC assembly leading to chemical modifications
6.4.1 Unique reactivity of silver NC toward TeNW
6.4.2 Atom exchange between Au NCs and Ag NPs
6.5 Summary and future perspective
References
Chapter 7 Cluster-based metal–organic
frameworks
7.1 Introduction
7.2 Synthesis approaches for silver metal-based MOFs
7.3 Structural features
7.3.1 One-dimensional coordinated structures
7.3.2 Two- and three-dimensional coordinated structures
7.4 Properties of nanocluster frameworks
7.4.1 Stability
7.4.2 Structure transformation
7.4.3 Absorption properties
7.4.4 Luminescence properties
7.4.5 Single-to-dual emission transformation
7.4.6 Computational studies
7.5 Applications
7.5.1 Sensing
7.5.2 Dual-function luminescence switching
7.6 Summary and future perspectives
References
Chapter 8 Synthesis of atomically precise clusters
8.1 Introduction
8.2 Synthesis techniques of gold and silver nanoclusters
8.2.1 Brust–Schiffrin method
8.2.2 Modified Brust methods
8.2.3 Ligand exchange induced structural transformation
(LEIST)
8.2.4 Solid-state synthesis
8.2.5 High-temperature synthesis
8.2.6 Other notable techniques
8.3 Synthetic techniques of gold and silver alloy nanoclusters
8.3.1 Coreduction method
8.3.2 Metal exchange method
8.3.3 Ligand exchange method
8.3.4 Metal deposition method
8.3.5 Intercluster reactions
8.4 Synthesis of nanoclusters with larger core (>100 metal atoms)
8.4.1 Au102(p-MBA)44
8.4.2 Au191(TBBT)66
8.4.3 Au246(p-MBT)80
8.4.4 Au∼2000(SR)∼290
8.5 Summary and future perspectives
References
Chapter 9 Chromatography and separation in nanocluster science
9.1 Introduction
9.2 Various techniques used for the separation of NCs
9.2.1 Brief history of PAGE
9.2.2 Brief history of chromatography
9.3 Principle, instrumentation, and procedure of various separation techniques
9.3.1 Poly acrylamide gel electrophoresis
(PAGE)
9.3.2 High-performance liquid chromatography
9.3.3 Thin layer chromatography
(TLC)
9.4 Earlier studies on the separation of atomically precise nanoclusters
9.5 Separation of hydrophilic nanoclusters
9.5.1 PAGE
9.5.2 Ion-pair chromatography
9.5.3 Hydrophilic interaction liquid chromatography
(HILIC)
9.6 Separation of hydrophobic NCs
9.6.1 Reversed phase-high performance liquid chromatography
(RP-HPLC)
9.6.2 Size exclusion chromatography
9.6.3 Chiral chromatography
9.6.4 Thin layer chromatography
(TLC)
9.7 Toward preparative scale separation of atomically precise nanoclusters
9.7.1 Preparative scale size exclusion chromatography
(PSEC)
9.7.2 Preparative thin layer chromatography
(PTLC)
9.8 Summary and future perspectives
References
Chapter 10 Mass spectrometry of atomically precise clusters
10.1 Introduction
10.2 Various techniques for ionization of NCs
10.2.1 Matrix-assisted laser desorption ionization
(MALDI)
10.2.2 Electrospray ionization
10.3 Instrumentation
10.4 Mass spectrometry of ligand-protected metal NCs
10.4.1 Gold NCs
10.4.2 Silver NCs
10.4.3 Other metal NCs
10.4.4 Alloy NCs
10.4.5 Isotopically pure NCs
10.5 Mass spectrometry of adducts of NCs
10.6 Tandem mass spectrometry of NCs
10.6.1 Collision-induced dissociation
10.6.2 Surface-induced dissociation
10.7 Ion mobility mass spectrometry of NCs
10.7.1 Principle and instrumentation
10.7.2 Separation of gas-phase isomers and aggregates of NCs
10.7.3 Determining structures of NCs from IM MS
10.8 Mass spectrometry of metal NCs in macromolecular templates
10.9 Mass spectrometry of larger NCs
10.10 Summary and future perspectives
References
Chapter 11 Spectroscopy of gas phase cluster ions
11.1 Introduction
11.2 Trapped ion electron diffraction
11.2.1 Theory and instrumentation
11.2.2 Structure determination
11.3 Ion mobility spectrometry
(IMS)
11.3.1 Instrumentation and fundamentals
11.3.2 IMS of bare nanoclusters
11.3.3 IMS of protected nanoclusters
11.4 Dissociation mass spectrometry
11.4.1 Dissociation of bare cluster ions
11.4.2 Dissociation of ligated cluster ions
11.5 Spectroscopic methods
11.5.1 Photo-dissociation
(PD) and UV-vis spectroscopy
11.5.2 Photoelectron spectroscopy
11.5.3 IR spectroscopy
11.6 Summary and future perspectives
References
Chapter 12 Structure by single crystal X-ray diffraction
12.1 Introduction
12.1.1 Importance of crystal structures
12.1.2 Challenges
12.1.3 Developments
12.2 Crystallization
12.2.1 Slow evaporation
12.2.2 Solvent diffusion
12.2.3 Vapor diffusion
12.2.4 Solvothermal
12.3 Basic core structural building blocks
12.3.1 Face-centered cubic structures
12.3.2 Body-centered cubic structures
12.3.3 Hexagonal structures
12.3.4 Icosahedron
12.3.5 Tetrahedron
12.3.6 Decahedron
12.4 Growth of building blocks
12.4.1 Fusion
12.4.2 Layer by layer
12.5 Surface structure
12.6 Crystal structures of archetypal nanoclusters
12.6.1 Gold nanoclusters
12.6.2 Silver nanoclusters
12.7 Cocrystals
12.8 Summary and future perspectives
References
Chapter 13 Electron microscopy of clusters
13.1 Introduction
13.2 Microscopy of naked clusters
13.3 Imaging structures using Cs corrected—TEM and single
particle reconstruction
13.4 Electron micro-diffraction and nanobeam electron diffraction
13.5 Challenges and precautions in measurements
13.6 Analytical procedures for improved data collection
13.7 Beyond electron microscopes
13.8 Summary and future perspective
References
Chapter 14 Computational approaches for nanocluster science
14.1 Importance of computational approach in cluster science
14.2 Basics of computational methods and models
14.2.1 Density functional theory
14.2.2 Total energy and force methods
14.2.3 Force fields, classical molecular dynamics, and Monte Carlo methods
14.2.4 QM/MM and multiscale methods
14.2.5 Transition states and reaction pathways
14.2.6 TD-DFT and excited state methods
14.3 Electronic structure of monolayer protected nanoclusters from DFT
14.3.1 Electronic stability of nanoclusters
14.3.2 Superatom model
14.3.3 Valence electron count and models for the shell-closing number
14.3.4 Projection of orbitals onto superatomic states
(PDOS)
14.3.5 Nonsuperatomic nanoclusters
14.4 Structural prediction of nanoclusters
14.5 Spectroscopic property calculations
14.5.1 Optical absorption spectroscopy
14.5.2 Emission and luminescence spectra
14.5.3 Mechanism of luminescence and its enhancements
14.5.4 Vibrational circular dichroism spectra
14.5.5 Raman spectra
14.5.6 Surface plasmon
14.6 Catalysis and other property calculations
14.6.1 Catalytic mechanisms
14.6.2 Magnetic properties
14.6.3 Electrochemical properties
14.6.4 Thermodynamic and vibrational properties of nanoclusters
14.7 Summary and future perspectives
References
Chapter 15 Ag and Au nanoclusters
15.1 Introduction
15.2 Journey from bulk to atomically precise nanoclusters
15.2.1 The color difference in bulk Ag/Au metals
15.2.2 Color tunability in Ag/Au nanoparticles (3–100 nm)
15.2.3 Color exhibition in Ag/Ag NCs (1–3 nm)
15.2.4 Melting properties of bulk to nanoclusters via nanoparticles
15.2.5 Magnetic properties of bulk to nanoclusters via nanoparticles
15.2.6 Transformation of crystal structures from bulk-to-nanoparticles-to-nanoclusters
15.2.7 Variation of band structures from bulk to nanoclusters
15.2.8 Calculation of transformation of plasmonic to nanoclusters
15.2.9 Quantum confinement in thiolated-Ag and Au nanoclusters
15.3 Types of Ag and Au nanoclusters based on surface coverage
15.3.1 Gas phase clusters
15.3.2 Nanoclusters in inorganic templates
15.3.3 Monolayer protected nanoclusters
15.3.4 Polymer protected nanoclusters
15.3.5 Biological scaffold templated nanoclusters
15.3.6 Nanoclusters in emulsions
15.3.7 Nanoclusters with hydrides and sulfides
15.4 Stability of atomically precise thiolate-protected Ag/Au NCs
15.4.1 Decomposition pathways: fission or fusion
15.4.2 Comparison of stability of Ag/Au NCs
15.4.3 Effect of e-beam
15.4.4 Solvent polarity
15.4.5 Surface effects
15.4.6 Electronic stability
15.4.7 Geometric stability
15.4.8 Steric stability
15.4.9 Thermal stability
15.4.10 Oxidation state
5.4.11 Photostability
15.5 Nomenclature of nanoclusters
15.6 Summary and future perspectives
References
Chapter 16 Alloy nanoclusters
16.1 Introduction
16.1.1 General introduction of alloy
16.1.2 Alloy nanotechnology from the ab initio perspective
16.1.3 Alloy nanoparticles and nanoclusters
16.2 Various synthetic methodologies
16.2.1 Co-reduction
16.2.2 Metal exchange
16.2.3 Metal deposition
16.2.4 Ligand exchange
16.2.5 Interparticle reactions
16.2.6 Reaction of nanoclusters with bulk metal
16.3 Structures of alloy nanoclusters
16.3.1 Gold-rich alloys
16.3.2 Silver-rich alloys
16.3.3 Copper-rich alloys
16.4 Properties of multimetallic nanoclusters
16.4.1 Optical properties
16.4.2 Chirality
16.4.3 Magnetism
16.5 Summary and future perspectives
References
Chapter 17 Naked clusters and ion chemistry of clusters
17.1 Introduction
17.2 Types of naked clusters
17.2.1 Metal clusters
17.2.2 Semiconductor clusters
17.2.3 Ionic clusters
17.2.4 Rare gas clusters
17.2.5 Molecular clusters
17.2.6 Cluster molecules
17.3 Mass spectrometry as a primary characterization technique of naked clusters
17.3.1 Synthesis of naked clusters using various cluster sources
17.3.2 Cluster growth and generation of cluster ions
17.3.3 Synthesis of naked clusters from different precursors and ionization techniques
17.3.4 Detection and analysis of naked clusters
17.3.5 Reactivity of naked clusters in the gas phase
17.3.6 Catalysis in gas phase
17.4 Other characterization methods of naked clusters
17.5 Solid-supported metal clusters/cluster assembled materials
17.6 Summary and future perspectives
References
Chapter 18 Atomic precision in other nanocluster systems: Chalcogenides
18.1 Introduction
18.2 Synthetic approaches for copper and silver chalcogenide NCs
18.2.1 Chalcogenide NCs from silylated chalcogenide sources
18.2.2 CS2 as chalcogen source
18.2.3 Chalcogen release by the C–S bond cleavage
18.3 Structure and properties of copper and silver chalcogenide clusters
18.3.1 Structure
18.3.2 Optical properties
18.3.3 Thermal properties
18.4 Tetrahedral nanoclusters of cadmium and zinc
18.4.1 Series of tetrahedral nanoclusters
18.4.2 Synthesis and crystallization
18.4.3 Optical properties
18.4.4 Hybrid materials based on tetrahedral NCs
18.5 Amine-protected magic sized nanoclusters
18.5.1 Synthesis and properties
18.5.2 Structure
18.6 Nanoclusters of Co, Ni, and Mn chalcogenides
18.6.1 Solution-phase synthesis of NCs
18.6.2 Structural characterization
18.6.3 Assembly of NCs into hierarchical solids
18.6.4 Collective properties
18.7 Understanding of chalcogenide NCs through mass spectrometry
18.8 Summary and future perspectives
References
Chapter 19 Other metal nanoclusters
19.1 Significance of other metal nanoclusters
(OMNCs)
19.2 Diverse synthetic strategies for OMNCs
19.3 Selected properties of OMNCs
19.3.1 Cu nanoclusters
19.3.2 Pt nanoclusters
19.3.3 Pd nanoclusters
19.3.4 Ir nanoclusters
19.4 Summary and future perspectives
References
Chapter 20 Thiols as ligands and structural control of nanoclusters
20.1 Introduction
20.2 Origin of monolayer thiol-protected precision nanoclusters
20.2.1 Thiol-protected gold nanoclusters
20.2.2 Thiol-protected silver nanoclusters
20.3 Surface functionalization of nanoclusters via ligand replacement reaction
20.4 Surface modification of nanoclusters via functional transformation chemistry
20.4.1 EDC/DCC coupling
20.4.2 Click reaction
20.5 Chemistry of surface ligands
20.5.1 Photochemistry
20.5.2 Electrochemistry
20.5.3 Optical chirality
20.5.4 Catalysis
20.6 Long-range colloidal assembly
20.6.1 Hydrogen bonding and electrostatic interactions
20.6.2 Van der Waals interactions
20.6.3 C–Hπ/π π interactions
20.6.4 Amphiphilicity
20.6.5 Light-triggered assembly
20.6.6 Coordination-assisted assembly
20.6.7 Template-assisted assembly
20.7 Summary and future perspectives
References
Chapter 21 Hydrides, alkynyls, phosphines, and amines as ligands for nanoclusters
21.1 Introduction
21.1.1 Hydrides
21.1.2 Alkynyls
21.1.3 Phosphines and amines
21.2 Atomic precision in labile ligand protected clusters
21.2.1 Simple clusters
21.2.2 Clusters of clusters
21.2.3 APCs with uncoordinated sites
21.3 Characterization
21.3.1 Single crystal neutron diffraction
(SCND)
21.3.2 Infrared spectroscopy
21.3.3 NMR spectroscopy
21.3.4 ESI mass spectrometry
21.4 Chemical and photophysical properties
21.5 Significance of hydrogen, phosphines, and alkynyls
21.6 Summary and future perspectives
References
Chapter 22 Clusters for biological applications
22.1 Introduction
22.2 Selection of the nanoclusters for biological application
22.2.1 Interactions of NCs with biological systems
22.2.2 Cellular uptake and in vivo distribution
22.2.3 Renal clearance
22.3 Biomedical applications
22.3.1 Biomolecular sensing
22.3.2 Bioimaging
(in vitro and in vivo)
22.4 Therapeutic applications
22.5 Other applications
22.5.1 Self-vaccine
22.5.2 Intrauterine device
22.5.3 Cancer biomarker detection
22.5.4 Anticancer activity
22.5.5 Antimicrobial agent
22.5.6 Enzymatic activity
22.6 Summary and future perspective
References
Chapter 23 Atomically precise clusters: What next?
References
Appendix
Index
Back cover