Design of Multi-center Multi-step Multi-redox Organic and Metallic Hybrid Molecules

近年来，由于制备新的π共轭材料并在材料科学中应用，对包含多个氧化还原中心的分子的研究在材料科学领域引起了相当大的研究兴趣。此外，这种分子具有两个以上的氧化还原活性金属中心是一个从根本上有吸引力的目标，通过混合价态来自这些多金属系统的多电子转移过程的研究。另一方面，通过使用含有第16族元素的5π-和7π-电子骨架设计新颖的氧化还原活性有机中心的兴趣引导我们探索合成新的含有硫和/或硒原子的5元杂环。因此，我们设计了2，3-二取代苯并[B]噻吩和1，3-二取代苯并[c]硫族化合物作为阴极和阳极多重氧化还原活性有机-金属有机杂化分子。2，3-二取代苯并[B]噻吩 ...更多信息 已经分别从苯并[B]噻吩或邻苯二甲酰氯作为起始原料系统地和选择性地合成了苯、1，3-二取代的苯并[c]噻吩和1，3-二取代的苯并[c]硒。通过物理和光谱手段和X射线晶体学分析进行分子的表征。含芳基片段的硫族元素衍生物的循环伏安图显示了由异常稳定的5π硫族元素自由基阳离子和7π硫族元素自由基阴离子衍生的明确的可逆阳极和阴极步骤。含二茂铁基片段的新型硫属元素衍生物的循环伏安图显示了一个明确的可逆阴极步骤和两个不同的可逆阳极步骤，前者来自异常稳定的7π硫属元素自由基阴离子，后者来自彼此被噻吩杂环隔开的二茂铁阳离子。用电子自旋共振（ESR）方法测定了几种新型7π硫属自由基阴离子的自由基性质。少

In recent years, the study of molecules comprising multiple reduction-oxidation (redox) centers have attracted considerable research interest in the field of material science due to the preparation of new π-conjugated materials with application in material science. Moreover, this kind of molecule having more than two redox-active metal centers is a fundamentally attractive target for the study of multi-electron transfer processes via the mixed valence state derived from these multi-metallic systems. On the other hand, interest in the design of novel redox-active organic centers by the use of a 5π- and 7π-electron framework containing group 16 elements has led us to explore the synthesis of new 5-membered heterocycles containing sulfur and/or selenium atom(s). Therefore, we have designed 2,3-disubstituted benzo[b]thiophene and 1,3-disubstituted benzo[c]chalcogenophene as both cathodic and anodic multiple-redox active organic-organometallic hybrid molecules. 2,3-Disubstituted benzo[b]thi … More ophenes, 1,3-disubstituted benzo[c]thiophenes, and 1,3-disubstituted benzo[c]selenophene have been systematically and selectively synthesized from benzo[b]thiophene or phthaloyl dichloride as a starting material, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the chalcogenophene derivatives containing aryl fragments showed well-defined reversible both anodic and cathodic steps derived from the unusually stable 5π chalcogenophene radical cations and 7π chalcogenophene radical anions. The cyclic voltammograms of the novel chalcogenophene derivatives containing ferrocenyl fragments showed a well-defined reversible cathodic step derived from the unusually stable 7π chalcogenophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene-heterocycle. The radical character of several novel 7π chalcogenophene radical anions was measured by ESR spectroscopy. Less