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Computational Modeling of Metal-Metal Interactions in Inorganic Complexes Using DFT Methods
Computational Modeling of Metal-Metal Interactions in Inorganic Complexes Using DFT Methods
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202105143
- ISBN
- 9798293855100
- DDC
- 546
- 서명/저자
- Computational Modeling of Metal-Metal Interactions in Inorganic Complexes Using DFT Methods
- 발행사항
- [Sl] : The University of Wisconsin - Madison, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 193 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-03, Section: B.
- 주기사항
- Includes supplementary digital materials.
- 주기사항
- Advisor: Berry, John F.
- 학위논문주기
- Thesis (Ph.D.)--The University of Wisconsin - Madison, 2025.
- 초록/해제
- 요약The electronic structure and bonding of inorganic complexes has always been of interest to the chemical community, especially in more complicated systems, such as in systems with metal-metal interactions. Recently, density functional theory (DFT) methods have been utilized to help better understand these complicated inorganic systems. In this work, I will showcase the versatility of these approaches to better understand the magnetic and spectroscopic behavior of inorganic complexes, to explain the bonding in these complexes, and to predict desirable complexes exhibiting new features in their electronic structure. In Chapter, 1 DFT calculations for Ru2M(dpa)4Cl2 (dpa = dipyridylamine) (M = Mn, Fe, Co, Mo, Tc, Re, W, Os) were used to determine the ground spin states of these complexes, and for the subset of (M = Mo, Tc, Re, W, Os), we show the formation of new Ru-M bonds, surpassing the strength of the starting material's Ru-Ru bond. In Chapter 2, the synthesis of dicolbalt paddlewheel complexes using acetate equatorial ligands and ether axial ligands is shown. These complexes were investigated using SQUID magnetometry, giving a J value of -31.7 cm-1. Broken symmetry (BS)-DFT calculations show that the magnetic exchange pathway is a function of both Co-Co distance and of Co-Co-L ( L = axial ligand) angle. It is also shown that these complexes are competent for carbene reactivity. In Chapter 3 we show the synthesis of a novel hexa-iron complex. This complex was analyzed using bond valence sum (BVS) analysis , DFT calculations, Mossbauer spectroscopy and electrochemical data to give the formulation of [Fe6O2(OH)(H3L)L], with nominally four Fe(II) ions and two Fe(III) ions. In Chapter 4, the synthesis of complexes of the form Mo2M(dedpa)4Cl2 (dedpa = diethyl-dipyridylamine) (M = Cr, Mn, Fe, Co, Ni) is explored. These complexes are shown to be more electron rich, easier to oxidize, and, interestingly, the impact of the ethyl substituents is not applied equally to all three metal. Additionally, the mechanism of ligand rearrangement is explored by DFT, showing that combating forces of ligand rearrangement energy and the interaction energy between the metals and the equatorial ligands drives the energetic barrier for ligand rearrangement.
- 일반주제명
- Inorganic chemistry
- 일반주제명
- Materials science
- 일반주제명
- Analytical chemistry
- 일반주제명
- Computational chemistry
- 키워드
- Broken symmetry
- 기타저자
- The University of Wisconsin - Madison Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-03B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520260202105143
■006m o d
■007cr#unu||||||||
■020 ▼a9798293855100
■035 ▼a(MiAaPQ)AAI32240943
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a546
■1001 ▼aPankratz, Trey C.
■24510▼aComputational Modeling of Metal-Metal Interactions in Inorganic Complexes Using DFT Methods
■260 ▼a[Sl]▼bThe University of Wisconsin - Madison▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a193 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-03, Section: B.
■500 ▼aIncludes supplementary digital materials.
■500 ▼aAdvisor: Berry, John F.
■5021 ▼aThesis (Ph.D.)--The University of Wisconsin - Madison, 2025.
■520 ▼aThe electronic structure and bonding of inorganic complexes has always been of interest to the chemical community, especially in more complicated systems, such as in systems with metal-metal interactions. Recently, density functional theory (DFT) methods have been utilized to help better understand these complicated inorganic systems. In this work, I will showcase the versatility of these approaches to better understand the magnetic and spectroscopic behavior of inorganic complexes, to explain the bonding in these complexes, and to predict desirable complexes exhibiting new features in their electronic structure. In Chapter, 1 DFT calculations for Ru2M(dpa)4Cl2 (dpa = dipyridylamine) (M = Mn, Fe, Co, Mo, Tc, Re, W, Os) were used to determine the ground spin states of these complexes, and for the subset of (M = Mo, Tc, Re, W, Os), we show the formation of new Ru-M bonds, surpassing the strength of the starting material's Ru-Ru bond. In Chapter 2, the synthesis of dicolbalt paddlewheel complexes using acetate equatorial ligands and ether axial ligands is shown. These complexes were investigated using SQUID magnetometry, giving a J value of -31.7 cm-1. Broken symmetry (BS)-DFT calculations show that the magnetic exchange pathway is a function of both Co-Co distance and of Co-Co-L ( L = axial ligand) angle. It is also shown that these complexes are competent for carbene reactivity. In Chapter 3 we show the synthesis of a novel hexa-iron complex. This complex was analyzed using bond valence sum (BVS) analysis , DFT calculations, Mossbauer spectroscopy and electrochemical data to give the formulation of [Fe6O2(OH)(H3L)L], with nominally four Fe(II) ions and two Fe(III) ions. In Chapter 4, the synthesis of complexes of the form Mo2M(dedpa)4Cl2 (dedpa = diethyl-dipyridylamine) (M = Cr, Mn, Fe, Co, Ni) is explored. These complexes are shown to be more electron rich, easier to oxidize, and, interestingly, the impact of the ethyl substituents is not applied equally to all three metal. Additionally, the mechanism of ligand rearrangement is explored by DFT, showing that combating forces of ligand rearrangement energy and the interaction energy between the metals and the equatorial ligands drives the energetic barrier for ligand rearrangement.
■590 ▼aSchool code: 0262.
■650 4▼aInorganic chemistry
■650 4▼aMaterials science
■650 4▼aAnalytical chemistry
■650 4▼aComputational chemistry
■653 ▼aDensity functional theory
■653 ▼aMetal-metal interactions
■653 ▼aMagnetic exchange
■653 ▼aEthyl substituents
■653 ▼aBroken symmetry
■690 ▼a0488
■690 ▼a0486
■690 ▼a0794
■690 ▼a0219
■71020▼aThe University of Wisconsin - Madison▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g87-03B.
■790 ▼a0262
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17359593▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
