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
• 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
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/491289713?language=en
• 关键词: Mixed; valent; macrocyclic; ruthenium; complexes

This project has two main goals: 1) The synthesis and comprehensive investigation of macrocyclic tri- and tetraruthenium complexes with strong electronic coupling in their mixed-valent oxidation states. For this purpose, we will employ self-complementary monoruthenium complex building blocks with hemilabile, heterocyclic chelate ligands, which offer uninterrupted pi-conjugation between the ethynyl group and the respective chelating, coordinating functionality. 2) The direct assessment of the electrical conductivity of these molecular, conductive loops. For these experiments, we will employ a home-built, STM-based setup for single molecule measurements that we fabricated according to the construction plan of our esteemed colleague Latha Venkataraman. This instrumentation was successfully put into operation in 2019 and has provided results that equal those obtained by expert groups in this field. To these ends, we will use anchor group-modified, macrocyclic complexes from project 1) as well as new anchor-group-modified derivatives of literature-known macrocycles with proven, high charge delocalization in mixed-valent states. The anchor groups are required to ensure that the test molecules bind to the nanoscale gold electrodes of the STM setup. This will put us into a position to successfully address the fundamental questions of how electronic coupling through space or through chemical bonds compare with regard to the efficiency of charge transport at the molecular level and whether the availability of two conduction paths makes metallacyclic structures superior to their linear analogs. The availability and successful implementation of a STM break junction setup in a strong synthetic group puts us in an ideal position to tackle such fundamental and largely unanswered questions. If successful, this project will put us at the forefront within the molecular conductance community.

本项目主要有两个目标：1）合成和研究混合价态下具有强电子耦合的大环三、四环钌配合物。为此，我们将采用自互补的单钌络合物构建块与半不稳定的，杂环螯合配体，其提供乙炔基和相应的螯合，配位功能之间的不间断的π-共轭。2)直接评估这些分子的导电性，导电环。对于这些实验，我们将采用一个自制的，基于STM的单分子测量装置，我们根据我们尊敬的同事Latha Venkataraman的建设计划制造。该仪器于2019年成功投入运行，并提供了与该领域专家组相同的结果。为此，我们将使用来自项目1）的锚基团改性的大环络合物以及文献已知的大环的新的锚基团改性的衍生物，其在混合价态中具有经证实的高电荷离域性。需要锚基团以确保测试分子结合到STM装置的纳米级金电极。这将使我们能够成功解决以下基本问题：通过空间或通过化学键的电子耦合如何比较分子水平上的电荷传输效率，以及两种导电路径的可用性是否使金属环结构优于它们的线性类似物。上级。在一个强大的合成组中，STM中断连接设置的可用性和成功实施使我们处于一个理想的位置，以解决这些基本的和基本上没有答案的问题。如果成功，这个项目将使我们在分子电导社区的最前沿。