Preparation and Assemblization of Highly Functionalized Organic Magnetic Molecules

有机磁性金属的开发是分子磁学研究的热点之一。在这样的自旋系统中，需要传导电子和局域自旋之间的自旋关联。我们设计了一系列作为候选分子的开壳给体作为这种自旋系统的组成部分。开壳施主是由一个施主和一个自由基单元构成的，当发生单电子氧化时，它们相互连接，形成一个交叉共轭的pi-体系。我们制备了两个以两个硝基氮氧化物为自由基单元和一个硫杂菲为给体单元的开壳给电子体异构体(2，7-和2，8-异构体)。SQUID测量表明，这些异构体在中性状态下分别为基态三重态和单重态。ESR研究表明，它们通过单电子氧化将基态多重数从三重态和单重态转变为两个四重态。还准备了三个以TTF为基础的开放式贝壳捐赠者。循环伏安和ESR测量表明，这些供体具有与母体供体相似的供体能力和开壳供体的电子学性质。这些结果表明，这些开壳供体满足有机磁性金属组分的要求之一。由这些自由基组成的混合价自由基离子盐的制备正在进行中。

Development of organic magnetic metals is one of the most interest investigation for molecular magnetism. In such spin system, it is required a spin correlation between conduction electrons and local spins. We designed a series of open-shell donors which are candidate molecules as components of such spin system. The open shell donors are constructed with a donor and a radical unit and they are connected so as to become a cross-conjugate pi-system when one-electron oxidation takes place. We prepared two open-shell donor isomers (2,7- and 2,8-isomer) composed of two nitronyl nitroxides as radical unit and a thianthrene as a donor unit. SQUID measurements showed that these isomers are ground state triplet and singlet in neutral state, respectively. The ESR study showed that they changes the ground state multiplicity from triplet and singlet to both quartet through one-electron oxidation. Three TTF-based open-shell donors were also prepared. Cyclic voltammetry and ESR measurement indicate that these donors have a similar donor ability to the mother donors and the electronic character as the open-shell donor. These results indicate that these open-shell donors satisfy one of required conditions for the components of organic magnetic metals. Preparations of mixed valent radical ion salts composed of these radicals are in progress.