Alkenylruthenium ferrocenyl and triarylamine conjugates for the quantitative analysis of electronic coupling in unsymmetrical mixed-valent compounds at the Class II/III borderline

烯基钌二茂铁基和三芳基胺缀合物用于定量分析 II/III 类边界不对称混合价化合物中的电子耦合

基本信息

项目摘要

This project aims at utilizing the radical cations of alkenyl- or styryl-modified ferrocenes and triarylamines to explore the borderline region between partial and full electron and spin delocalisation in unsymmetrical mixed-valent compounds. Both kinds of compounds feature two strongly coupled, yet chemically different redox sites, whose intrinsic redox potentials can be independently varied by the introduction of suitable substituents at the ferrocene or triarylamine subunit or the coligands at the ruthenium site. This will allow us to directly influence the vertical offset of the local minima on the potential hypersurface and hence the degree of valence delocalisation in the ground state of the corresponding mixed-valent radical cations. Furthermore, both redox-active subunits will offer indicative IR or EPR addressable spectroscopic tags which provide quantitative measures of the charge and spin densities at the respective sites at inherently different timescales. With these compounds in hand we will address the following issues:- How are the redox-splitting between the two redox waves and the degree of charge and spin delocalisation in the electronic ground state of the mixed-valent forms of these compounds affected by the difference in the intrinsic redox potentials of the individual sites?- Can we obtain a congruent picture of charge and spin density distributions over the individual redox sites by analyzing the spectroscopic shifts of different charge-sensitive IR markers and the analysis of the hyperfine splitting patterns to different spin density markers within these molecules?- How are the position, the intensity and the half-width of the low energy electronic absorption bands of the mixed-valent radical cations affected by the redox asymmetry?- Can we obtain a method for determining the effective charge-transfer distance in such mixed-valent systems by comparing the characteristic parameters of that electronic band with the quantitative information on charge and spin delocalisation derived from IR and EPR spectroscopy?- Can we identify environmental effects that control valence (de)localization and can we utilize them for switching from one to the other?
本计画旨在利用烯基或苯乙烯基修饰的二茂铁及三芳胺的自由基阳离子,探讨不对称混合价化合物中部分电子与全电子之间的边界区域及自旋离域。这两种化合物具有两个强耦合,但化学上不同的氧化还原位点,其固有的氧化还原电位可以独立地通过在二茂铁或三芳胺亚基或共配体在钌网站的引入合适的取代基而变化。这将使我们能够直接影响潜在的超曲面上的局部极小值的垂直偏移,从而影响相应的混合价自由基阳离子基态的价离域程度。此外,两种氧化还原活性亚基将提供指示性IR或EPR可寻址光谱标签,其提供在固有不同时间尺度的相应位点处的电荷和自旋密度的定量测量。有了这些化合物在手,我们将解决以下问题:-如何氧化还原分裂之间的两个氧化还原波和程度的电荷和自旋离域在电子基态的混合价形式的这些化合物的影响,在不同的内在氧化还原电位的个别网站?-我们能否通过分析不同电荷敏感IR标记物的光谱位移和这些分子内不同自旋密度标记物的超精细分裂模式的分析,获得单个氧化还原位点上电荷和自旋密度分布的一致图像?氧化还原不对称性如何影响混合价阳离子自由基低能电子吸收带的位置、强度和半宽?我们能否通过比较该电子带的特征参数与来自IR和EPR光谱的电荷和自旋离域的定量信息,获得一种确定这种混合价体系中有效电荷转移距离的方法?我们能否确定控制原子价(去)定域的环境效应,以及我们能否利用它们从一种转换到另一种?

项目成果

期刊论文数量(4)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine-Vinylruthenium Conjugates.
  • DOI:
    10.1021/acs.inorgchem.7b02186
  • 发表时间:
    2017-10
  • 期刊:
  • 影响因子:
    4.6
  • 作者:
    Christopher Hassenrück;R. Winter
  • 通讯作者:
    Christopher Hassenrück;R. Winter
Mixed-Valent Ruthenocene-Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites.
  • DOI:
    10.1021/acs.inorgchem.8b03253
  • 发表时间:
    2019-02
  • 期刊:
  • 影响因子:
    4.6
  • 作者:
    Christopher Hassenrück;André Mang;R. Winter
  • 通讯作者:
    Christopher Hassenrück;André Mang;R. Winter
Oxidized Styrylruthenium–Ferrocene Conjugates: From Valence Localization to Valence Tautomerism
  • DOI:
    10.1002/ejic.201600776
  • 发表时间:
    2017-01
  • 期刊:
  • 影响因子:
    2.3
  • 作者:
    Christopher Hassenrück;Philipp Mücke;Johanna Scheck;S. Demeshko;R. Winter
  • 通讯作者:
    Christopher Hassenrück;Philipp Mücke;Johanna Scheck;S. Demeshko;R. Winter
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Professor Dr. Rainer Winter其他文献

Professor Dr. Rainer Winter的其他文献

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{{ truncateString('Professor Dr. Rainer Winter', 18)}}的其他基金

Charge-Transfer Salts of Electron-Rich Diruthenium and Macrocyclic Tetraruthenium Complexes
富电子二钌和大环四钌配合物的电荷转移盐
  • 批准号:
    435877990
  • 财政年份:
    2019
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Platinum Complexes with Sigma bonded BODIPY, Aza-BODIPYS and Squaraines as Dual Emitters and photocatalysts
含有 Sigma 键合 BODIPY、Aza-BODIPYS 和方酸菁的铂络合物作为双发射体和光催化剂
  • 批准号:
    215611198
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Vinylruthenium-modified carbazoles, tetrathiafulvalenes and triarylmethyl-cations as highly efficient poyelectrochromics
乙烯基钌改性咔唑、四硫富瓦烯和三芳基甲基阳离子作为高效聚电致变色材料
  • 批准号:
    142603506
  • 财政年份:
    2009
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Metallorganische Oligophenylenvinylene: Synthese, Konjugation und Elektronentransfer
有机金属低聚亚苯基亚乙烯基:合成、共轭和电子转移
  • 批准号:
    5445394
  • 财政年份:
    2004
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Allenylidene complexes of ruthenium with hemilabil oxygen-, sulfur- or seleno ligants: syntheses, properties and applications to catalysis
钌与 hemilabil 氧、硫或硒配体的亚烯二烯配合物:合成、性质和催化应用
  • 批准号:
    5387877
  • 财政年份:
    2002
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Mixed-valent macrocyclic ruthenium complexes as conductive, molecular loops
作为导电分子环的混合价大环钌配合物
  • 批准号:
    491289713
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Research Grants

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Control of solution and aggrigation properties of ferrocenyl bola surfactant
二茂铁基博拉表面活性剂溶解和聚集特性的控制
  • 批准号:
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    2020
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二茂铁/二茂铁基官能化树枝状聚合物:合成、表征及其电化学行为
  • 批准号:
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  • 财政年份:
    2018
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Construction of supramolecular multi-ferrocenyl assemblies toward molecular devices using intramolecular charge distributions as information
使用分子内电荷分布作为信息构建分子器件的超分子多二茂铁基组件
  • 批准号:
    25790016
  • 财政年份:
    2013
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    --
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Electron transfer in Cobalt complexes using rigid ferrocenyl decorated polypyridyl based ligands
使用刚性二茂铁基修饰的聚吡啶基配体在钴配合物中进行电子转移
  • 批准号:
    231408045
  • 财政年份:
    2013
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Cyclic ferrocenyl intercalator as a novel probe for gene polymorphism analysis
环状二茂铁嵌入剂作为基因多态性分析的新型探针
  • 批准号:
    13680672
  • 财政年份:
    2001
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Preparation of Chiral ferrocenyl Chalcogenides and their Application to asymmetric Synthesis
手性二茂铁硫属化物的制备及其在不对称合成中的应用
  • 批准号:
    10650853
  • 财政年份:
    1998
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    --
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Development of Chiral Ferrocenyl Compounds including Hetero Atoms and Their Use in Asymenetric Synthesis
含杂原子的手性二茂铁基化合物的开发及其在不对称合成中的应用
  • 批准号:
    09450340
  • 财政年份:
    1997
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    --
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2,6-Dimethoxyphenyl Derivatives of a Variety of Elements
2,6-二甲氧基苯基多种元素的衍生物
  • 批准号:
    08455429
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    1996
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Arrangements, Reactivities and Functions of Organic and Organometallic Molecules in Inorganic Layred Spaces
无机层状空间中有机和有机金属分子的排列、反应性和功能
  • 批准号:
    06640721
  • 财政年份:
    1994
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Synthesis of Ferrocenyl Polyphosphazenes from Silicon-Nitrogen-Phosphorus Compounds (Chemistry)
由硅氮磷化合物合成二茂铁基聚磷腈(化学)
  • 批准号:
    8409023
  • 财政年份:
    1984
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