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Silver(I) and Copper(I) Complexes from Homoleptic to Heteroleptic: Synthesis, Structure and Characterization

A plethora of novel scientific phenomena and practical applications, such as solid-state molecular solar cells and other optoelectronic devices for energy harvesting and lighting technologies, have catalyzed us to synthesize novel compounds with tunable properties. Synthetic routes, single crystal structures, and spectral and materials properties are described. Reactions of Ag(I) and Cu(I) precursors with various types of ligands -- including the azolates, diimines, and diiphosphines -- lead to the corresponding complexes in high yield. Varying the metal ions, ligands, synthetic methods, solvents, and/or stoichiometric ratio can change the properties including the molecular geometry or packing structure, reactivity, photophysical and photochemical properties, semiconducting behavior, and/or porosity of the functional coordination polymers obtained. For solar cells purposes, the absorption energy can be extended from the ultraviolet (UV) region, through the entire visible (Vis) region, onto a significant portion of the near-infrared (NIR) portion of the solar spectrum with high absorption coefficients due to the infinite conjugation of Cu(I) with diimine ligands. Twenty-eight crystal structures were obtained by conventional crystal growth methods from organic solvents, whereas their bulk product syntheses also included "green chemistry" approaches that precluded the use of hazardous organic solvents. The resulting products are characterized by powder x-ray diffraction (PXRD), Fouriertransform infrared (FTIR), nuclear magnetic resonance (NMR), UV/Vis/NIR absorption/diffuse reflectance/photoluminescence spectroscopies, and thermogravimetric analysis (TGA). Regarding the scientific phenomena investigated, the highlighting work in this dissertation is the discovery of novel bonding/photophysical/optoelectronic properties of the following materials: a black absorber with absorption from 200- 900 nm, a very stable compound with a bright green luminescence obtained by a solventless reaction, and a novel coordination polymer showing uncommon interaction of Ag(I) with three different types of diimine ligands simultaneously.

Identiferoai:union.ndltd.org:unt.edu/info:ark/67531/metadc1404512
Date12 1900
CreatorsAlmotawa, Ruaa Mohammed
ContributorsOmary, Mohammad A., Cundari, Thomas R., D'Souza, Francis, Golden, Teresa D.
PublisherUniversity of North Texas
Source SetsUniversity of North Texas
LanguageEnglish
Detected LanguageEnglish
TypeThesis or Dissertation
Formatxiv, 232 pages, Text
RightsPublic, Almotawa, Ruaa Mohammed, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved.

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