Redox-switchable magnetic materials based on triarylamine functionalized coordination polymers

该项目旨在构建由顺磁性金属离子片段和氧化还原活性三芳基胺连接体组成的强大的磁性可切换配位网络，这是配位网络的一种未知功能。新材料的制备基于我们小组建立的合成方法。它们的功能变化将在现有的磁性配位聚合物的基础上进一步开发。的基本架构是基于柱层系统组成的2-D网络的顺磁性金属离子片段和氧化还原活性的三芳基接头结合适当的ditopic间隔配体。后者能够将附加功能引入到3-D网络中。主要感兴趣的单元是氧化还原活性的三芳基连接基，其可以容易地转化为阳离子自由基，如我们已经在分子组装中所示。自由基连接体的形成导致2-D和3-D磁性结构，这取决于配位网络的底层结构。该项目旨在研究如何在两个基础网络结构中控制自由基连接体的氧化形成。实现这一点的基本选择是（i）化学氧化或（ii）电化学氧化和（iii）将合适的电子受体作为客体分子包含到孔中。此外，将探索用三芳基胺接头和电子受体作为双位间隔配体的组合产生供体-受体聚集体的可能性，其可以直接或经由另外并入孔中的光敏剂光学地解决。的磁性，电化学和光学性能，必要的材料的预期功能，将进行彻底的调查和他们的解释支持基于DFT和从头算方法的理论计算。

The project aims to build robust magnetically switchable coordination networks consisting of paramagnetic metal ion fragments and redox-active triarylamine-based linkers, a yet unknown functionality for coordination networks. The preparation of the new materials is based on synthetic methods established in our group. Their functional variation will be further developed on the basis of already available magnetic coordination polymers. The fundamental architecture is based on pillared-layer systems composed of 2-D networks of paramagnetic metal ion fragments and redox-active triaryl linkers combined with appropriate ditopic spacer ligands. The latter enables to introduce additional functionalities into the 3-D networks. The unit of primary interest is the redox-active triaryl linker, which can be easily converted into a cationic radical, as we have already shown in molecular assemblies. The formation of radical linkers leads to 2-D and 3-D magnetic structures, depending on the underlying architecture of the coordination network. This project aims to investigate how the oxidative formation of radical linkers can be controlled in the two underlying network architectures. Fundamental options to achieve this are (i) the chemical or (ii) electrochemical oxidation and (iii) the inclusion of suitable electron acceptors as guest molecules into the pores. In addition, the possibility of generating donor-acceptor aggregates with a combination of triarylamine linkers and electron acceptors as ditope spacer ligands will be explored, which can be optically addressed either directly or via photosensitizers additionally incorporated in the pores. The magnetic, electrochemical, and optical properties, essential for the intended functionality of the materials, will be thoroughly investigated and their interpretation supported by theoretical calculations based on DFT and ab initio methods.