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

批准号：
281314146
负责人：
Professor Dr. Rainer Winter
金额：
--
依托单位：
Arbeitsgruppe Anorganische Chemie: Organometallchemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2015
资助国家：
德国
起止时间：
2014-12-31 至 2018-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/281314146?language=en
关键词：
Alkenylruthenium ferrocenyl triarylamine conjugates quantitative

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?

该项目旨在利用烷基或苯乙烯或苯乙烯基修饰的铁胶烯和三级氨的自由基阳离子在不对称的混合变量化合物中探索部分和全电子之间的边界区域以及自旋分离式化合物。两种化合物都具有两种强烈耦合但化学上不同的氧化还原位点，它们的固有氧化还原电位可以通过在二陈代或三元氨基亚基或ruthenium位置的三院或三生叶亚基或coligands引入合适的取代基来独立地变化。这将使我们能够直接影响局部最小值的垂直抵消潜在的超表面，从而在相应的混合价值自由基阳离子的基础状态下的价离域的程度。此外，两个氧化还原活性亚基都将提供指示性的IR或EPR可寻址光谱标签，这些标签可在固有不同的时间表上提供电荷和自旋密度的定量度量。借助这些化合物，我们将解决以下问题： - 两种氧化还原波之间的氧化还原分解以及这些化合物的混合价值形式的电子接地状态的氧化还原程度以及由单个站点的固有氧化还原电位的差异所影响的这些化合物的混合形式的差异？不同电荷敏感的IR标记物以及对这些分子内不同旋转密度标记的超精细分裂模式的分析？ - 低能电子吸收束的低能电子吸收束的位置，强度和一半是如何通过对这种有效的距离进行比较的方法来确定有效的距离的方法，以确定有效的距离吗？具有源自IR和EPR光谱的电荷和自旋定位的定量信息的电子条带吗？