Synthesis and Spectroscopic Characterization of Low- to High-Valent Weak-Field Lanthanide Complexes

dc.contributor.advisor La Pierre, Henry S.
dc.contributor.author Gompa, Thaige P.
dc.contributor.committeeMember Sadighi, Joseph P.
dc.contributor.committeeMember Wilkinson, Angus P.
dc.contributor.committeeMember Zhang, John
dc.contributor.committeeMember Soper, Jake D.
dc.contributor.committeeMember Mourigal, Martin
dc.contributor.department Chemistry and Biochemistry
dc.date.accessioned 2023-01-10T16:09:59Z
dc.date.available 2023-01-10T16:09:59Z
dc.date.created 2021-12
dc.date.issued 2021-11-01
dc.date.submitted December 2021
dc.date.updated 2023-01-10T16:10:00Z
dc.description.abstract Redox chemistry and valence electronic structure of the lanthanides in molecular complexes is a rapidly expanding field of research. The contemporary understanding of the accessible oxidation states of the lanthanide elements and the variability in their electronic structure is the result of several groundbreaking fundamental discoveries. While the lanthanide elements have already found widespread use in technical and consumer applications, the continued reevaluation of basic redox properties is a central chemical concern to establish a more complete description of periodic properties. This continuous development of understanding of valence electronic structure and its connection to oxidation state and coordination environment is essential for the continued development of lanthanides in quantum information science and quantum materials research. Due, in part, to the minimal extension of the valence 4f orbitals in lanthanide complexes, covalent bonding and electronic communication between metal centers, in particular lanthanide-lanthanide metal centers, is nearly non-existent and unexplored. This thesis details the development of new methodology for lanthanide triiodide starting materials for salt metathesis reactions. This thesis also outlines the development of novel lanthanide complexes that exhibit unique electronic structure properties such as vibronic coupling in neutral divalent complexes and intervalence charge transfer in mixed-valent, homobimetallic complexes. Additionally, the first isostructural molecular valences series spanning three oxidation states (Eu2+, Gd3+, and Tb4+) is synthesized and interrogated through high-field and -frequency electronic paramagnetic resonance. This work correlates formal charge, zero-field splitting, and covalency in these lanthanide complexes.
dc.description.degree Ph.D.
dc.format.mimetype application/pdf
dc.identifier.uri http://hdl.handle.net/1853/70032
dc.language.iso en_US
dc.publisher Georgia Institute of Technology
dc.subject Lanthanides
dc.subject f-Block
dc.subject Redox Chemistry
dc.subject High-Valent
dc.subject Low-Valent
dc.subject Electron Paramagnetic Resonance
dc.subject HFEPR
dc.subject Mixed-Valent
dc.subject Intervalence Charge Transfer
dc.subject IVCT
dc.title Synthesis and Spectroscopic Characterization of Low- to High-Valent Weak-Field Lanthanide Complexes
dc.type Text
dc.type.genre Dissertation
dspace.entity.type Publication
local.contributor.advisor La Pierre, Henry S.
local.contributor.corporatename School of Chemistry and Biochemistry
local.contributor.corporatename College of Sciences
relation.isAdvisorOfPublication 31d0dff7-a4d7-44f5-b39e-ebdd20cbfdf4
relation.isOrgUnitOfPublication f1725b93-3ab8-4c47-a4c3-3596c03d6f1e
relation.isOrgUnitOfPublication 85042be6-2d68-4e07-b384-e1f908fae48a
thesis.degree.level Doctoral
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