Advances in Metallacrown Chemistry

Preface
Acknowledgments
Contents
Contributors
Host–Guest Chemistry of Metallacrowns
1 Molecular Recognition in Macrocycles
1.1 Organic Recognition Agents
1.2 Metallacrowns
1.3 Binding Larger Metals
2 Building up Systems of Greater Complexity
3 15-MC-5 Host–Guest Chemistry
3.1 Central Ion as Guest in 15-MC-5
3.2 15-MC-5 Structures
3.3 Anion Recognition
3.4 Porous Structures
3.5 Measuring Guest Affinities
4 Conclusion
References
Aspects of NMR Characterization of Metallacrowns
1 Introduction
1.1 Pulsed-Gradient Spin-Echo NMR
1.2 1H-NMR of Paramagnetic Complexes
1.3 1H-NMR of Lanthanide Complexes
2 Interaction of Metallacrowns with Inorganic and Organic Anions
2.1 Interaction of Mn(III) Metallacrowns with Anions
2.2 Interaction of Copper(II) 15-MC-5 with Monocarboxylates
2.3 Formation of Dimeric Capsules
3 Metal Exchange Equilibria
3.1 Metal Exchange in Manganese(II/III) 12-MC-4 Complexes
3.2 Metal Exchange in Copper(II) 12-MC-4 and 15-MC-5 Complexes
4 MC Rearrangements and Ligand Exchange
4.1 MC Expansion
4.2 Ligand Exchange in Copper(II) Metallacrowns
5 Ln(III)/Mn(III) and Ln(III)/Cu(II) MCs: Insight on Their Structure in Solution
5.1 Ln(III)/Mn(III) 12-MC-4 Complexes
5.2 Ln(III)/Cu(II) 15-MC-5 Complexes
6 Conclusions
References
Influence of the Hydroxamate Ligands’ Structure on the Thermodynamic Properties and Structure of Metallacrown Complexes
1 Introduction
2 Hydroxamate Derivatives as Ligands for MCs
2.1 Acid–Base Properties
3 Self-assembly of Metallacrown Complexes
3.1 Metallacrown Structural Paradigm
4 Thermodynamic Properties of Metallacrown Complexes
4.1 Cu(II) Complexes
4.2 Ni(II) Complexes
4.3 Zn(II) Complexes
5 Structural Studies
5.1 MC Complexes Based on Hydroxamates Functionalized with O-Donors in β-Position
5.2 MC Complexes Based on α-Functionalized Hydroxamates
6 Metallacrowns Building Blocks
References
Metallacrowns as DNA Binders
1 DNA as a Target for Ligand Binding
2 Analytical Techniques for Studying Ligand/DNA Interactions
3 Metallacrown Complexes with DNA
3.1 Metallacrowns as Double-Stranded DNA Ligands
3.2 Metallacrowns as G4 DNA Ligands
4 Conclusions
References
Magnetic Metallacrowns: From Randomness to Rational Design
1 Introduction
1.1 Molecular Magnetism
1.2 Synthetic Strategies for Preparing Molecular Magnets
1.3 Single-Molecule, Single-Ion, and Single-Chain Magnets
2 Metallacrowns
2.1 Structural Control of Metallacrowns
3 Pseudo-Metallacrowns with Single-Molecule Magnetic Properties
3.1 28-MC-10: DyIII6MnIII4MnIV2, the First Mn-4f Single-Molecule Magnet
3.2 22-MC-8: DyIII4MnIII6Displays Slow Magnetic Relaxation
3.3 16-MC-6: DyIII4MnIII4 Displays Slow Magnetic Relaxation
3.4 26-MC-8: Lanthanide Choice Leads to Different Magnetic Responses
3.5 14-MC-5: The Development of Planar Metallacrowns as SMMs
3.6 12-MC-4, 16-MC-6, and 20-MC-7: Using Diamagnetic Ring Metals to Probe Lanthanide Coupling
4 Single-Molecule Magnetic Metallacrowns
4.1 12-MC-4s
4.2 15-MC-5s
References
Beyond the Metallacrown: Controlling First- and Second-Order Coordination Spheres Towards Discrete and Extended Architectures
1 An Introduction to Discrete Host–guest Assemblies Centred on Metallacrown Host Units
2 Fluoro-Centred Host Metallacrowns and Their Guest Enticing Abilities
2.1 Hexacopper Fluoro Azametallacrown Cavitands as Hosts for Cationic Guests
2.2 Guest Binding Within F-bridged Octametallic 16-MCCr(III)-8 [Cr8] Metallacrowns
2.3 Heterometallic [Cr(III)7M(II)] (M = Mn, Fe, Co, Ni, Zn, Cd and Mg) Metallacrowns (and Variations on the Theme)
3 Organometallic 12-MCM(III)-3 (M = Ru, Rh, Ir) Metallacrown Hosts
3.1 Redox Responsive 12-MCM(III)-3 (M = Ru, Rh) Metallacrown Li+ and Na+ Receptors
3.2 The Accommodation of F-containing Guests Within 12-MCM(III)-3 (M = Ru, Rh, Ir) Metallacrowns
3.3 Selective Li+ Ion Detection in Water and Serum
3.4 The Role of a 16-Membered Metallacrown in the Interconversion of Two Nanocages
4 Controlling the First Coordination Sphere Towards Selective Binding and Topology Control
4.1 Hexametallic 18-MCCu(II)-6 Pertechnetate and Perrhenate Scavengers
4.2 Pentanuclear 12-MCCu(II)-4 Metallacrowns as Building Blocks Towards 1- and 2-D Extended Networks
4.3 Inverse Metallacrowns and Inverse Crown Ether Complexes
4.4 Triple Decker Inverse 12-MCCu(I)-pz-4 Azametallacrowns
4.5 An Inverse 9-MCCu(II)-3 Metallacrown as Host to an Anti-Inflammatory
4.6 Inverse Crown Ether Complexes and Their Solid-State Hosting Abilities
5 Concluding Remarks
References
Water-Soluble 15-Metallacrown-5 Complexes: Molecular Structures and Properties
1 Introduction
2 15-MC-5 Structural Paradigm
2.1 Computational Study of the Formation Process
3 Synthetic Approaches to Aqua Complexes
3.1 Structures of Aminohydroximate Ln(III)–Cu(II) 15-MC-5 Aqua Complexes
4 Solution-State Behavior
4.1 Toward MRI Applications
4.2 Toward Hydrothermal Single-Source Precursors of Nanomaterials
5 New Similarities and Analogues: Bi(III) Versus Ln(III)
References
Metallacrown-Based Catalysts for Water Oxidation and CO2 Conversion
1 Water Oxidation
2 CO2 Conversion
3 Summary
References
A Structural Examination of Metallacrowns with Main Group Elements in the Ring Positions
1 Introduction
2 Gallium-Containing Metallacrown Complexes
2.1 Gallium 12-MC-4 Structures
2.2 Gallium 12-MC-4 Dimer Structures
2.3 Non-standard Gallium-Containing Metallacrowns and Metallacryptates
3 Other Main Group Metallacrown Complexes
3.1 Aluminum-Containing Metallacrowns and Metallacryptates
3.2 Tellurium-Containing Metallacrowns
3.3 Tin-Containing Metallacrowns
4 Azametallacrown Complexes with Main Group Elements
4.1 Gallium and Indium Azametallacrowns
4.2 Other p-Block Azametallacrowns—Aluminum, Silicon, and Tin
4.3 Alkali Metal Azametallacrowns—Lithium and Sodium
5 Conclusion
References
Index