基于四硫富瓦烯及其衍生物的有机自旋电子材料的制备及性质研究

New multifunctional molecular materials possessing both electrical and magnetic properties, such as magnetic semiconductors or magnetic conductors, have received increasing interest due to their important application in molecular spintronics. Some advantages for molecular magnetic semiconductors are smaller volume, lower density, easy complexing and processing. Moreover, they can be crystalline materials and obtained by molecular design and rational synthesis, which makes the further studies possible for the relation of structure and functionalities. Magnetic semiconductor with high magnetic ordering temperature (Tc) is currently one of the challenging research for synthetic chemist. We will focus our studies on organic spintronic materials based on paramagnetic metal complexes including Tetrathiafulvalene (TTF) and its derivatives. Firstly, we design and synthesis some new pai-conjugated and electrochemically active TTF ligands, which are used to link magnetic centers to form interesting structures (multinuclear or polymeric metal complexes). After crystal engineering and Inorganic-Organic hybrid methods, new multifunctional molecular materials, such as magnetic semiconductors or electronically-switchable spin crossover compounds, will be prepared and used for the device fabrication. The effective spin injection into the organic system and to increase Pi-d interactions in the complexed materials will be also investigated in these spintronic materials.

兼具铁磁性和导电性质的自旋电子材料(如磁性半导体)是当前材料学家研究的重要目标之一。分子磁性半导体具有体积小、相对密度低、易于复合加工等特点，可由分子设计合成并得到单晶材料，从而进一步开展功能与结构相关性的研究。高临界温度分子磁性半导体的制备是当前合成化学家的挑战性研究之一。本项目关注有机自旋电子材料（重点是金属配合物），集中开展以四硫富瓦烯（TTF）或其衍生物为骨架的顺磁性金属配合物以及电荷转移化合物的研究。首先进行含四硫富瓦烯及其衍生物的有机配体设计，进一步引入顺磁性金属离子或自由基等，利用晶体工程和无机-有机杂化等方法，获得具有铁磁性和导电双功能性质的有机自旋电子材料，如铁磁性半导体、导电自旋转换材料等。期望增强材料内部长程磁耦合及磁电作用，进而利用有机材料具有低自旋散射和长自旋扩散长度的优点，制备出具有较强自旋相关效应的铁磁/有机复合材料。

高性能有机自旋电子材料研发，是在分子水平上实现自旋电子器件与应用的关键之一。本项目围绕基于四硫富瓦烯及其衍生物的有机自旋电子材料的制备与应用开展了较为深入的研究：设计合成了一系列新型含四硫富瓦烯衍生物的-共轭有机配体，引入过渡金属离子、稀土金属离子或自由基等顺磁性物质，合成了多系列电荷转移型金属配合物和有机共价材料。制备了具有较高质子和电子导电性的二维金属有机框架材料，开展了顺磁性自由基二维电荷转移配合物的合成与光热转化性能研究；在磁性和导电双功能有机自旋电子材料研究中，构建了一系列含四硫富瓦烯基元的稀土金属簇配位聚合物，利用氧化还原过程可以调控单分子磁体性能；研究了介电（导电）和自旋转换具有协同作用的多功能分子材料；制备了双氮负离子桥联电荷转移配合物，具有较为有效的光催化固氮与转化性能。项目实施过程中在Nat. Chem. (1篇)，Sci. Adv. (1篇)，J. Am. Chem. Soc. (3篇)，Angew. Chem. Int. Ed. (2篇)，Matter (1篇)等国际学术期刊上发表论文20余篇，授权发明专利1 项。项目的实施为后续制备和开发新型电荷转移型有机自旋电子材料提供了理论和实验基础。