Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing
Previous work was successful at delineating reaction pathways for the photoactivated synthesis of an amine, [CztBu(PyriPr)(NH2−PyriPr)], by double intramolecular C−H activation and functionalization via irradiating a metal(II) azido complex, [CztBu(PyriPr)2NiN3. The present work seeks to expand upon...
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ftunivnotexas:info:ark/67531/metadc2137532 2024-01-07T09:45:50+01:00 Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing Alamo Velazquez, Domllermut C. Cundari, Thomas Valsson, Omar Wang, Hong Richmond, Michael Lee, Wei-Tsung 2023-05 Text https://doi.org/10.12794/metadc2137532 https://digital.library.unt.edu/ark:/67531/metadc2137532/ English eng University of North Texas local-cont-no: submission_3259 doi:10.12794/metadc2137532 https://digital.library.unt.edu/ark:/67531/metadc2137532/ ark: ark:/67531/metadc2137532 Public Alamo Velazquez, Domllermut C. Copyright Copyright is held by the author, unless otherwise noted. All rights Reserved. organometallics qubit nickel cobalt iron quantum computing Gaussian ORCA photocatalysis photochemistry photophysics C-H activation excited states phosphorescence computational chemistry Chemistry Inorganic Physical Thesis or Dissertation 2023 ftunivnotexas https://doi.org/10.12794/metadc2137532 2023-12-09T23:08:11Z Previous work was successful at delineating reaction pathways for the photoactivated synthesis of an amine, [CztBu(PyriPr)(NH2−PyriPr)], by double intramolecular C−H activation and functionalization via irradiating a metal(II) azido complex, [CztBu(PyriPr)2NiN3. The present work seeks to expand upon earlier research, and to substitute the metal with iron or cobalt, and to expand the study to photocatalyzed intermolecular C−H activation and functionalization of organic substrates. Density functional theory (DFT) – B3LYP/6-31+G(d') and APFD/Def2TZVP – and time-dependent density functional theory (TDDFT) were used to propose a detailed pathway comprised of intermediates of low, intermediate, or high spin multiplicity and photo-generated excited states for the reaction of the azido complex, [CztBu(PyriPr)2MN3] to form the amine complex [CztBu(PyriPr)M(NH2−PyriPr)], M = Co, Ni or Fe, and the intermediates along the reaction pathway. For applications on quantum computing, the photophysical properties of photoactive d8 nickel(II) complexes are modeled. Such systems take advantage of a two-level system pathway between ground to excited state electronic transitions and could be useful for the discovery of successful candidates for a room temperature qubit, the analogue of a classical computational bit. A modified organometallic model, inspired by a nitrogen vacancy selective intersystem crossing model in diamond, was developed to take advantage of the formation of excited states. Tanabe-Sugano diagrams predict areas where these excited states may relax via phosphorescent emission. Under Zeeman splitting, these transitions create the conditions required for a two-level system needed to design a functional organometallic qubit. Thesis Orca University of North Texas: UNT Digital Library |
institution |
Open Polar |
collection |
University of North Texas: UNT Digital Library |
op_collection_id |
ftunivnotexas |
language |
English |
topic |
organometallics qubit nickel cobalt iron quantum computing Gaussian ORCA photocatalysis photochemistry photophysics C-H activation excited states phosphorescence computational chemistry Chemistry Inorganic Physical |
spellingShingle |
organometallics qubit nickel cobalt iron quantum computing Gaussian ORCA photocatalysis photochemistry photophysics C-H activation excited states phosphorescence computational chemistry Chemistry Inorganic Physical Alamo Velazquez, Domllermut C. Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
topic_facet |
organometallics qubit nickel cobalt iron quantum computing Gaussian ORCA photocatalysis photochemistry photophysics C-H activation excited states phosphorescence computational chemistry Chemistry Inorganic Physical |
description |
Previous work was successful at delineating reaction pathways for the photoactivated synthesis of an amine, [CztBu(PyriPr)(NH2−PyriPr)], by double intramolecular C−H activation and functionalization via irradiating a metal(II) azido complex, [CztBu(PyriPr)2NiN3. The present work seeks to expand upon earlier research, and to substitute the metal with iron or cobalt, and to expand the study to photocatalyzed intermolecular C−H activation and functionalization of organic substrates. Density functional theory (DFT) – B3LYP/6-31+G(d') and APFD/Def2TZVP – and time-dependent density functional theory (TDDFT) were used to propose a detailed pathway comprised of intermediates of low, intermediate, or high spin multiplicity and photo-generated excited states for the reaction of the azido complex, [CztBu(PyriPr)2MN3] to form the amine complex [CztBu(PyriPr)M(NH2−PyriPr)], M = Co, Ni or Fe, and the intermediates along the reaction pathway. For applications on quantum computing, the photophysical properties of photoactive d8 nickel(II) complexes are modeled. Such systems take advantage of a two-level system pathway between ground to excited state electronic transitions and could be useful for the discovery of successful candidates for a room temperature qubit, the analogue of a classical computational bit. A modified organometallic model, inspired by a nitrogen vacancy selective intersystem crossing model in diamond, was developed to take advantage of the formation of excited states. Tanabe-Sugano diagrams predict areas where these excited states may relax via phosphorescent emission. Under Zeeman splitting, these transitions create the conditions required for a two-level system needed to design a functional organometallic qubit. |
author2 |
Cundari, Thomas Valsson, Omar Wang, Hong Richmond, Michael Lee, Wei-Tsung |
format |
Thesis |
author |
Alamo Velazquez, Domllermut C. |
author_facet |
Alamo Velazquez, Domllermut C. |
author_sort |
Alamo Velazquez, Domllermut C. |
title |
Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
title_short |
Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
title_full |
Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
title_fullStr |
Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
title_full_unstemmed |
Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing |
title_sort |
theoretical studies of photoactive metal complexes with applications in c-h functionalization and quantum computing |
publisher |
University of North Texas |
publishDate |
2023 |
url |
https://doi.org/10.12794/metadc2137532 https://digital.library.unt.edu/ark:/67531/metadc2137532/ |
genre |
Orca |
genre_facet |
Orca |
op_relation |
local-cont-no: submission_3259 doi:10.12794/metadc2137532 https://digital.library.unt.edu/ark:/67531/metadc2137532/ ark: ark:/67531/metadc2137532 |
op_rights |
Public Alamo Velazquez, Domllermut C. Copyright Copyright is held by the author, unless otherwise noted. All rights Reserved. |
op_doi |
https://doi.org/10.12794/metadc2137532 |
_version_ |
1787427465052815360 |