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Access Type
WSU Access
Date of Award
January 2024
Degree Type
Dissertation
Degree Name
Ph.D.
Department
Chemistry
First Advisor
Matthew M. Allen
Abstract
The stabilization of 5d orbitals in complexes of divalent lanthanide (LnII) ions relative to their trivalent lanthanide (LnIII) counterparts enables tuning of the optical and electrochemical properties of LnII ions by varying ligand field strength around LnII. This ability to control the properties of LnII ions has led to an increasing number of studies aimed at understanding the coordination chemistry of LnII for target applications such as lighting, photocatalysis, the design of medical imaging probes, and the design of sensors. However, many reported studies on the impact of ligand field on the structural, optical, and electrochemical properties of LnII ions have primarily focused on probing the impact of varying the type of donor atoms. Less attention has been devoted to understanding the impact of varying ligand denticity and steric hindrance on the structural, optical, and electrochemical properties of LnII ions. Thus, my PhD research is focused on addressing this gap in knowledge regarding the impact of ligand denticity and steric hindrance on the structural, optical, and electrochemical properties of LnII ions. Variation in ligand denticity and counterion identity generated complexes of LnII ions (Ln = Eu or Sm) with a wide range of coordination numbers (6–10) and geometries (octahedron, trigonal prism, capped trigonal prism, capped octahedron, triangular dodecahedron, hexagonal bipyramid, cube, capped cube, muffin, sphenocorona, staggered dodecahedron, and bicapped square antiprism). This variation in ligand field strength through changes in ligand denticity, steric factors, or donor atom identity enabled a broad range turnability of the emission colors of EuII from UV to yellow and trailing into orange (300–635 nm). In addition, changes in ligand field strength led to variation in the absorption properties of complexes of SmII from blue to near-IR of the electromagnetic spectrum. Furthermore, the electrochemical properties of two cryptates of SmII that differ only in the strength of Lewis basicity of amine donors revealed that increasing the strength of Lewis basicity of ligand donor atoms in a cryptate of SmII increases its reducing power. These findings describing the impact of ligand field on the structural, optical, and electrochemical provide critical insights for tailoring the design of new complexes of LnII ions with properties suitable to specific applications.
Recommended Citation
Bokouende, Sergely Steephen, "Coordination Chemistry Of Low-Valent Lanthanide Ions" (2024). Wayne State University Dissertations. 4015.
https://digitalcommons.wayne.edu/oa_dissertations/4015
