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