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Photo-Initiated Halide Release and O...

Turlington, Michael Davis.

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Photo-Initiated Halide Release and Oxidation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Photo-Initiated Halide Release and Oxidation./
Author:	Turlington, Michael Davis.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2021,
Description:	216 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-12, Section: B.
Contained By:	Dissertations Abstracts International82-12B.
Subject:	Inorganic chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28417008
ISBN:	9798515280789

Photo-Initiated Halide Release and Oxidation.
Turlington, Michael Davis.

Photo-Initiated Halide Release and Oxidation. - Ann Arbor : ProQuest Dissertations & Theses, 2021 - 216 p.

Source: Dissertations Abstracts International, Volume: 82-12, Section: B.

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2021.

This item must not be sold to any third party vendors.

The ability to control interactions between halides and molecular excited states is of importance in the fields of halide sensing and energy storage. The tools of supramolecular assembly provide a means for fundamental study, as ground-state preorganization precludes the need for diffusion of the short-lived excited states. This dissertation seeks to gain insight into how these assemblies respond to light excitation and to utilize these interactions for energy storage reactions. Towards this end, Chapter 1 briefly reviews strategies that have been developed for halide supramolecular assembly and halide oxidation.In Chapters 2 and 3, ruthenium polypyridyl complexes with hydrogen-bonding ligands that controlled the stoichiometry and thermodynamics of ground-state halide supramolecular assembly are presented. In Chapter 2, ancillary ligands are shown to induce an excited-state dipole that was oriented toward or away from the assembled halide. When the excited-state dipole was directed towards the halide, coulombic repulsion resulted in its photorelease. Orientation of the excited-state dipole away from the receptor ligand resulted in enhanced halide assembly. In Chapter 3, modifying the hydrogen bonding functional groups was found to tune the ground-state equilibrium constants over two orders of magnitude. In the excited-state, analysis of the photorelease kinetics suggested that the extent of hydrogen bonding with the halide presented a barrier to dissociation. In Chapter 4, ruthenium complexes with a novel hydrogen-bonding ligand formed 1:2 ruthenium:halide assemblies in organic solution. The excited-state reduction potentials (Ru2+*/+) were tuned by varying the electronic properties of the ancillary ligands. For the most potent photo-oxidant, the luminescent excited-state was statically and dynamically quenched by iodide. Both the static and dynamic components were sensitive to the iodide concentration, suggesting that the supramolecular assembly structure impacted the quenching mechanism.In Chapter 5, photocatalytic bromide oxidation at a metal-oxide interface in pH 5.6 aqueous electrolyte is investigated. To promote bromide oxidation under these challenging conditions, a dual-sensitizer photoanode was developed that coupled efficient electron injection and bromide oxidation by utilizing a separate reductant and oxidant as sensitizers. A reductive quenching reaction was identified as the primary energy loss pathway in the cell, but the yield was reduced through anode design.

ISBN: 9798515280789Subjects--Topical Terms:

3173556
Inorganic chemistry.
Subjects--Index Terms:

Excited states

Photo-Initiated Halide Release and Oxidation.
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245 1 0 $a Photo-Initiated Halide Release and Oxidation.
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300 $a 216 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-12, Section: B.
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502 $a Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2021.
506 $a This item must not be sold to any third party vendors.
520 $a The ability to control interactions between halides and molecular excited states is of importance in the fields of halide sensing and energy storage. The tools of supramolecular assembly provide a means for fundamental study, as ground-state preorganization precludes the need for diffusion of the short-lived excited states. This dissertation seeks to gain insight into how these assemblies respond to light excitation and to utilize these interactions for energy storage reactions. Towards this end, Chapter 1 briefly reviews strategies that have been developed for halide supramolecular assembly and halide oxidation.In Chapters 2 and 3, ruthenium polypyridyl complexes with hydrogen-bonding ligands that controlled the stoichiometry and thermodynamics of ground-state halide supramolecular assembly are presented. In Chapter 2, ancillary ligands are shown to induce an excited-state dipole that was oriented toward or away from the assembled halide. When the excited-state dipole was directed towards the halide, coulombic repulsion resulted in its photorelease. Orientation of the excited-state dipole away from the receptor ligand resulted in enhanced halide assembly. In Chapter 3, modifying the hydrogen bonding functional groups was found to tune the ground-state equilibrium constants over two orders of magnitude. In the excited-state, analysis of the photorelease kinetics suggested that the extent of hydrogen bonding with the halide presented a barrier to dissociation. In Chapter 4, ruthenium complexes with a novel hydrogen-bonding ligand formed 1:2 ruthenium:halide assemblies in organic solution. The excited-state reduction potentials (Ru2+*/+) were tuned by varying the electronic properties of the ancillary ligands. For the most potent photo-oxidant, the luminescent excited-state was statically and dynamically quenched by iodide. Both the static and dynamic components were sensitive to the iodide concentration, suggesting that the supramolecular assembly structure impacted the quenching mechanism.In Chapter 5, photocatalytic bromide oxidation at a metal-oxide interface in pH 5.6 aqueous electrolyte is investigated. To promote bromide oxidation under these challenging conditions, a dual-sensitizer photoanode was developed that coupled efficient electron injection and bromide oxidation by utilizing a separate reductant and oxidant as sensitizers. A reductive quenching reaction was identified as the primary energy loss pathway in the cell, but the yield was reduced through anode design.
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650 4 $a Chemistry. $3 516420
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653 $a Halide photorelease
653 $a Photoanode
653 $a Ruthenium polypyridyl
653 $a Supramolecular assembly
690 $a 0488
690 $a 0485
710 2 $a The University of North Carolina at Chapel Hill. $b Chemistry. $3 1021872
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