Download or read book Controlling Redox Processes in Metal Complexes and Multifunctional Materials written by Khrystyna Herasymchuk and published by . This book was released on 2020 with total page 207 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal complexes incorporating redox-active ligands have the potential to facilitate controlled multielectron chemistry, enabling their use in catalysis and energy storage applications. Moreover, the use of transition metal complexes containing redox-active ligands has been extended to two- (2D) and three-dimensional (3D) materials, such as supramolecular assemblies (i.e., metallacycles, molecular cages, or macrocycles) and metal-organic frameworks (MOFs) for catalytic, magnetic, electronic, and sensing applications. Salens (N2O2 bis(Schiff-base)-bis(phenolate) are an important class of redox-active ligands, and have been investigated in detail as they are able to stabilize both low and high metal oxidation states for the above-mentioned applications. The work in this thesis focuses on the synthesis and electronic structure elucidation of metal salen complexes in monomeric form, as discrete supramolecular assemblies and 3D MOFs. Structural and spectroscopic characterization of the neutral and oxidized species was completed using mass spectrometry, cyclic voltammetry, X-ray diffraction, NMR, UV-Vis-NIR, and EPR spectroscopies, as well as theoretical (DFT) calculations. Chapter 2 discusses the synthesis and electronic structure evaluation of a series of oxidized uranyl complexes, containing redox-active salen ligands with varying para-ring substituents (tBu, OMe, NMe2). Chapters 3 and 4 discuss the incorporation of a redox-active nickel salen complex equipped with pyridyl groups on the peripheral positions of the ligand framework into supramolecular structures via coordination-driven self-assembly. The self-assembly results in formation of a number of distinct metallacycles, affording di-, tetra-, and octa-ligand radical species. Finally, the design, synthesis, and incorporation of metal salen units into MOFs is discussed in Chapter 5. Preliminary assembly and oxidation experiments are presented as an opportunity to explore the redox-properties of salen complexes incorporated into a solid-state 3D framework. Overall, the work described in this thesis provides a pathway for salen ligand radical systems to be used in redox-controlled host-guest chemistry, catalysis, and sensing.