Organic high spin molecules, their metal complexation and mixed radical crystals

这一应用的目的是合成新的高自旋分子，可通过以下方式获得：·通过氮配位或通过自旋携带单元将稳定的有机高自旋自由基与金属络合物配位；·合成混合固体中性或自由基离子盐。在这个范围内，作为我们研究的一个新方向，我们计划集中精力研究具有两个或更多自由基中心的金属配体。这里的一个重要要求是可连接的分子应该保持在高自旋基态，即三重态或四重态。连接应使用含氮杂环，如吡啶、吡唑，甚至带有中性稳定自旋中心的联嘧啶，如硝基氮氧化物、氮氧化物或氧杂环。具有一个或多个未成对电子的典型金属离子，如Cu2+、Fe2+和Mn2+，应进行金属络合试验。为了预测上述体系的自旋态，将进行量子化学计算。有机自由基的计算将采用扩展CI、能带结构和密度泛函理论的AM1方法。对于金属络合物，密度泛函理论(DFT)和B3LYP泛函已显示出很好的结果，并将被系统地应用。

This application aims at the synthesis of new high spin molecules which can be obtained via : · Ligation of stable organic high spin radicals to metal complexes either by nitrogen coordination or through the spin carrying units; · Synthesis of mixed solid neutral or radical ion salts. In this scope, as a new direction of our research we plan to concentrate our efforts on metal ligatable ligands bearing two or more radical centers. An important requirement here is that ligatable molecules should persist in high spin ground state, i.e. triplet or quartet. Nitrogen containing heterocycles such as pyridine, pyrazole, or even bipyrimidines carrying neutral stable spin centres like nitronyl nitroxides, nitroxides, or oxo-verdazyls should be used for ligation. Typical metal ions with one or more unpaired electrons as Cu2+ , Fe2+ and Mn2+ shall be tested for metal complexation. To predict the spin states of the above systems, quantum chemical calculations will be performed. AM1 with extended CI, band structure calculations and density functional theory will be employed for the organic radicals. For the metal complexes, density functional theory (DFT) with the B3LYP functionals has shown to produce very good results and will employed systematically.