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首页> 外文期刊>Applied Magnetic Resonance >Trovacenyl-based organometallic triradicals: Spin frustration, competing interactions and redox splitting
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Trovacenyl-based organometallic triradicals: Spin frustration, competing interactions and redox splitting

机译：基于Trovacenyl的有机金属三基团：自旋受阻，竞争性相互作用和氧化还原分裂

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摘要

Two new triradicals based on trovacene [(eta(7)-tropylium)vanadium(eta(5)-cyclopentadienyl)], 1,3,5-tri([5]trovacenyl)benzene 4 and 1,3,5-tri([5]trovacenyl)-6-methoxybenzene 5 were prepared and their magnetic properties were studied by continuous-wave X-band electron paramagnetic resonance (EPR) spectroscopy and by temperature-dependent magnetic susceptometry. The EPR spectra of 4 and 5 in liquid toluene solution demonstrate that the three unpaired electrons localized on the vanadium atoms interact with each other in both complexes. The data from magnetic susceptometry revealed that the electron spins in both triradicals are anti ferromagnetically coupled despite the meta-phenylene bridge. The exchange coupling constants are equal in the C-3-symmetrical triradical 4 (J = J' = -0.68 cm(-1)), which leads to a twofold degenerate spin ground state (spin frustration). The symmetry lowering by methoxy substitution of the benzene spacer in 5 results in the effect of competing interactions (J = -1.83 cm(-1) and J' = -2.38 cm(-1)). In addition to magnetocommunication, the effect of ring substitution on electrocommunication is also discernable. It manifests itself in disparate redox splittings deltaE(1/2) (0/-, -/2-) and deltaE(1/2) (-/2-, 2-/3-) for 5, while these parameters are equal for the C-3-symmetrical trinuclear complex 4.
机译：两个新的基于自由基的三辛基[（eta（7）-tropylium）钒（eta（5）-环戊二烯基]]，1,3,5-三（[5] trovacenyl）苯4和1,3,5-tri（制备了[5] trovacenyl）-6-甲氧基苯5，并通过连续波X波段电子顺磁共振（EPR）光谱和温度依赖性磁化法研究了它们的磁性。液态甲苯溶液中4和5的EPR光谱表明，位于钒原子上的三个不成对的电子在两种络合物中都相互作用。来自磁化感受器的数据表明，尽管存在亚亚苯基桥，但两个三基团中的电子自旋都是反铁磁耦合的。交换耦合常数在C-3-对称三自由基4中相等（J = J'= -0.68 cm（-1）），这导致双重简并的自旋基态（自旋受挫）。苯间隔基在5中被甲氧基取代而降低的对称性导致竞争相互作用的影响（J = -1.83 cm（-1）和J'= -2.38 cm（-1））。除了磁通信之外，还可以识别环取代对电通信的影响。它表现为5的完全不同的氧化还原分裂deltaE（1/2）（0 /-，-/ 2-）和deltaE（1/2）（-/ 2-，2- / 3-），而这些参数相等C-3对称的三核复合物4。

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