Groundbreaking progress in molecule-based optoelectronic devices for lighting, display and energy-harvesting technologies demands highly efficient and easily processable functional materials with tunable properties governed by their molecular/supramolecular structure variations. To date, functional coordination compounds whose function is governed by non-covalent weak forces (e.g., metallophilic, dπ-acid/dπ-base stacking, halogen/halogen and/or d/π interactions) remain limited. This is unlike the situation for metal-free organic semiconductors, as most metal complexes incorporated in optoelectronic devices have their function determined by the properties of the monomeric molecular unit (e.g., Ir(III)-phenylpyridine complexes in organic light-emitting diodes (OLEDs) and Ru(II)-polypyridyl complexes in dye-sensitized solar cells (DSSCs)). This dissertation represents comprehensive results of both experimental and theoretical studies, descriptions of synthetic methods and possible application allied to monovalent coinage metal-based functional materials. The main emphasis is given to the design and synthesis of functional materials with preset material properties such as light-emitting materials, light-harvesting materials and conducting materials.
In terms of advances in fundamental scientific phenomena, the major highlight of the work in this dissertation is the discovery of closed-shell polar-covalent metal-metal bonds manifested by ligand-unassisted d10-d10 covalent bonds between Cu(I) and Au(I) coinage metals in the ground electronic state (~2.87 Å; ~45 kcal/mol). Moreover, this dissertation also reports pairwise intermolecular aurophilic interactions of 3.066 Å for an Au(I) complex, representing the shortest ever reported pairwise intermolecular aurophilic distances among all coinage metal(I) cyclic trimetallic complexes to date; crystals of this complex also exhibit gigantic luminescence thermochromism of 10,200 cm-1 (violet to red). From applications prospective, the work herein presents monovalent coinage metal-based functional optoelectronic materials such as heterobimetallic complexes with near-unity photoluminescence quantum yield, metallic or semiconducting integrated donor-acceptor stacks and a new class of Au(III)-based black absorbers with cooperative intermolecular iodophilic (I…I) interactions that sensitize the harvesting of all UV, all visible, and a broad spectrum of near-IR regions of the solar spectrum. These novel functional materials of cyclic trimetallic coinage metal complexes have been characterized by a broad suit of spectroscopic and structural analysis methods in the solid state and solution.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc1011848 |
| Date | 08 1900 |
| Creators | Ghimire, Mukunda Mani |
| Contributors | Omary, Mohammad A., 1969-, D'Souza, Francis, Slaughter, LeGrande M., Richmond, Michael G., Balch, Alan L. |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | xxiv, 293 pages, Text |
| Rights | Public, Ghimire, Mukunda Mani, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved. |
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