四嗪-Fe(III)配合物的合成及室温电化学诱导自旋态转变研究

Great efforts have been devoted into the electric effect induced complex spin state switching, which is the basis of the electrically controlled molecular junction, due to the fascinating memory properties and great potential applications in the molecular level electrical devices. It is a straightforward strategy to achieve the electric effect induced spin transition of a complex through electrochemistry induced spin state switching, but seldom experimental result was reported probably ascribed to the limited to the lack of a suitable complex system. This project proposes to investigate the electrochemistry induced spin state switching in s-tetrazine-Fe(III) complexes. First of all, based on the theoretical calculation-assisted design and synthesis of ligands, s-tetrazine-Fe(III) complexes would be prepared with the rationally designed coordination structures, and an optimization of the electric performance would be employed. Then, combining theoretical calculations, mathematical modeling and experimental characterizations of complexes would also be applied to reveal the impact of ligand structure on the electronic arrangement changes and spin state switching of the complex during electrochemical redox process. Finally, a program would be established to select and optimize the structure and electrical performance of related complexes, to realize the electrochemistry induced spin state switching in s-tetrazine-Fe(III) system. The results of this project would provide not only theoretical and experimental support for developing a straightforward method of electric effect induced complex spin state switching, but also new materials for further development of molecular level electronic components based on the complexes possessing spin state switching properties.

电效应诱导配合物的自旋态改变，是电控分子结的基础，在分子级电子电路中有巨大的应用前景。电化学诱导自旋态转变，是一种直接简便地实现电效应诱导自旋态转变的方法，但限于缺乏合适的配合物体系，还没有实验研究的报道。本项目提出在四嗪-Fe(III)配合物中开展电化学诱导自旋态转变的研究，包括筛选设计合成四嗪配体；控制四嗪-Fe(III)配合物的结构，优化配合物的性质；结合理论计算、数学建模和实验研究，揭示配体结构对配合物在电化学氧化还原过程中的电子排布和自旋态变化的影响规律；建立一种筛选和优化相关配合物结构和性质的方法，实现电化学诱导四嗪-Fe(III)配合物的自旋态转变。本项目的开展，将为发展一种相对简单高效的电效应诱导配合物自旋态转变的新方法提供理论和实验支撑，为进一步开发基于配合物自旋态转变的分子级电子元器件提供一种新材料。

电化学诱导过渡金属配合物发生自旋态转变，是一种直接调控分子自旋状态的思路，实现方法一直备受关注。本项目计划在含四嗪结构配体的配合物体系中开展相关研究，通过理论计算与实验验证相结合的方式，研究分子结构与直接调控之间的内在联系，完成了对含四嗪配体结构的理论计算筛选、完成了四嗪化合物的合成条件优选、初步开展了含四嗪结构配合物的合成等，得到了一些结果.合作开展了面向化学战剂降解的Zr类二维MOF的制备和性能研究，开发了微波辅助快速制备方法，实现了高时空效能的制备，具有进一步扩大生产的潜力，研究了二维MOF微观结构对催化降解二甲氧基-4-硝基苯基磷酸酯的影响，发现调节二维MOF中Zr或Hf簇附近的封端结构，可以显著加快降解，实现了约2min的降解反应半衰期。