【作者】 王超；

【导师】 廖代正；

【作者基本信息】 南开大学 ， 无机化学， 2012， 博士

【摘要】 近年来，金属-自由基配合物表现出异常磁学性质，因此受到了人们越来越多的关注。大量的自由基-金属配合物被人们采用不同的方法合成出来，并且得到了较为完善的表征。但是，迄今为止，人们对于金属-自由基配合物的结构和自由基本身配位点多少的关系仍然不是很清楚。因此，在本论文中，作者合成了含不同配位点的十类自由基，并与金属离子进行配位，得到了38个具有不同结构的金属-自由基配合物，对其进行了结构和变温磁化率的表征，并采用不同的理论模型评估和讨论了配合物内不同种类的自旋载体间的磁相互作用。在本论文中，作者采用了三种不含功能性配位点的自由基与金属的六氟乙酰丙酮盐配位，得到了六个单核三自旋的配合物和三个一维链状的配合物，其中，使用双自由基和铜（II）的六氟乙酰丙酮盐合成了一个具有一维梯状链的配合物。当采用含有一个功能性配位点的自由基时，得到了23个金属-自由基配合物，绝大部分具有双核四自旋的平行四边形的框架，其中，与镝（III）的噻吩甲酰三氟丙酮盐配位时，得到了一个在低温区具有交流虚部信号的一维链状配合物，表明该配合物具有慢弛豫的行为；另一个与铜（II）的六氟乙酰丙酮盐所形成的配合物具有罕见的小振幅的自旋转换行为。当采用含有两个功能性配位点的自由基时，得到了4个过渡金属-自由基的配合物，其中，作者通过使用喹喔啉基取代的Ullman型氮氧自由基与铜（II）的六氟乙酰丙酮盐进行配位时，得到了一个三核五自旋的体系。通过比较得到的38个金属-配合物的结构，当自由基上的功能性配位点增多时，一般来说，其所形成的配合物有结构变复杂的趋势。更多还原

【Abstract】 In recent years, metal-radical complexes have been attracted much moreattention due to their unusual magnetic properties. A large number of metal-radicalcomplexes had been synthesized using different methods and had been characterizedperfectly. However, up to now, the relationship between the structure of metal-radicalcomplexes and the number of coordination sites in radical ligands are not too clear.Thus, in this paper,38metal-radical complexes were synthesized with differentstructures using ten kinds of nitronyl nitroxide radicals, and characterized structurallyand magnetically. Many methods are also used to evaluate the magnetic interactionsbetween the spin carriers in these complexes.In this paper, three kinds of non-functional radicals were employed to coordinatewith metal-hfac moieties, resulting six mononuclear tri-spin complexes and three onedimensional complexes. Among them, a one dimensional ladder-like complex wasprepared based on biradical and copper-hfac moiety. When four kinds of radicals withone functional coordination site were used,23metal-radical complexes were obtainedwith mostly binuclear four-spin rectangle structure. During these complexes, a onedimensional complex was obtained with signal in χ” measurements when the hfacwas replaced with tfa, suggesting slow magnetic relaxtion in this complex; incomplex25, a small amplitude spin transition behavior (Tc=80K, ΔTc=50K, Δμeff=0.23B.M.) has been observed, only few examples have been reported. However, whenthe radicals with two functional coordination sites were employed to coordinate withmetal ion, four transitional metal-radical complexes were obtained. It is worth notingthat a trinuclear five-spin complex was synthesized using quinoxalinal substitutednitronyl nitroxide radical and copper-hfac moiety.Comparing structures of these38metal-radical complexes, we see that in general,the more functional coordination sites radical ligands has, more complicate structureits complexes has.更多还原