Chemical, Electrochemical and Physical Properties of Metallosupramolecular Architectures with Tetrazine Based Ligands Including Investigations of Anion-pi Interactions

在这个由化学学部大分子、超分子和纳米化学项目资助的项目中，德州农工大学的Kim Dunbar将研究阴离子π相互作用的各个方面：阴离子与芳香分子的相互作用。目标是研究含有电正四嗪环的配体的金属配合物，这些配体形成不寻常的分子环组合，包括五元五边形，在溶液中具有高稳定性和显著的灵活性，可以通过添加不同的阴离子很容易地转化为其他大小的环。另一个目标是研究由阴离子的捕获或释放引发的化学反应，这可能是改变组件的物理和化学性质的一种方法。来自固态、溶液、气相和计算研究的数据将用于评估阴离子π力的强度，并协助未来旨在预测结构的实验。这项研究的一个应用将是通过使用五元环分子作为构建块来设计非常大的多面体分子。另一个应用将是利用四嗪配体易于还原的优势来制备有机自由基，这些有机自由基可以作为顺磁性金属离子之间的桥梁来构建分子磁铁。这项研究的更广泛影响包括培养化学科学方面的研究生和博士后研究人员，努力扩大未被充分代表的群体参与化学科学研究，以及与当地博物馆和科学展览联系，以加强科学和技术的了解。该项目所需的技能的多样性为学生提供了一个学习广泛研究学科的绝佳机会。在这个项目中，有机分子和金属离子的组装将被用来促进大型几何结构的形成，这些结构通常可以显示出对应用有用的不同寻常的特性。这项工作将扩大化学的曲目，可用于从分子成分开始创造磁性和导电材料。这些研究的结果可能对磁性材料重要的各种应用产生许多重要的长期影响，包括非易失性存储器和自旋电子学。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Kim Dunbar of the Texas A&M University will study various aspects of anion-pi interactions: anion interactions with aromatic molecules. The goals are to study metal complexes with ligands containing electropositive tetrazine rings that form unusual molecular ring assemblies including five-membered pentagons exhibiting high stabilities in solution and remarkable flexibility that allows them to be easily converted to other ring sizes by the addition of different anions. Another goal is to study chemical reactions triggered by the capture or release of anions which may be a way to alter the physical and chemical properties of the assemblies. Data from solid-state, solution, gas phase and computational studies will be used to assess the strength of anion-pi forces and to assist in future experiments aimed at predicting structures. One application of this research will be to design very large polyhedral molecules by using the five-membered ring molecules as building blocks. Another application will be to construct molecular magnets by taking advantage of the ease of reduction of tetrazine ligands to prepare organic radicals that can act as bridges between paramagnetic metal ions. The broader impacts of the research include graduate student and postdoctoral researcher training in the chemical sciences, efforts to broaden the participation of underrepresented groups in chemical science research, and outreach to local museums and science fairs in order to enhance scientific and technological understanding. The versatility of skills required to work on the project presents an excellent opportunity for students to learn about a broad spectrum of research disciplines. In this project the assembly of organic molecules and metal ions will be harnessed to promote the formation of large geometric structures that often can display unusual properties useful for applications. This work will expand the repertoire of chemistry that can be used to create magnetic and conducting materials starting with molecular components. The results of these studies could have many important long term impacts on a variety of applications in which magnetic materials are important, including non-volatile memory and spintronics.