School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Inorg Chem. 2009 Nov 2;48(21):10264-74. doi: 10.1021/ic901379d.
A series of multistate redox-active architectures has been synthesized, structurally characterized, and their optical and redox properties investigated. Specifically, two redox-active ferrocene or cobalt-dithiolene moieties have been introduced to the "bay" region of perylene-bisimides. Three of these disubstituted perylene-bisimide species have been structurally characterized by single crystal X-ray diffraction, confirming the twisted nature of the central perylene core. The first isomeric pair of disubstituted perylene-bisimide isomers, N,N'-di-(n-butyl)-1,7-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (2) and N,N'-di-(n-butyl)-1,6-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (3), structurally characterized by single crystal X-ray diffraction are reported and compared. Structural characterization of the cobalt-dithiolene substituted perylene-bisimide, N,N'-di-(n-butyl)-1,7-dicyclopentadienyl-cobalt(II)-dithiolenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (4), reveals the expected twisting of the perylene core and confirms the ene-dithiolate geometry of the cobalt dithiolene moiety. Cyclic voltammetry measurements, coupled with spectroelectrochemcial and electron paramagnetic resonance studies, of 1-4, where 1 is N,N'-di-(n-butyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide, reveal the two anticipated perylene-bisimide based reductions. In addition, for the ferrocene substituted compounds, 1-3, a single reversible two-electron oxidation is seen with only a small degree of communication between the ferrocene groups observed in the 1,6-isomer where the two ferrocene groups are attached to the same naphthyl moiety. In the case of 4, two reversible reductions associated with the cobalt-dithiolene moieties are observed, confirming communication across the reduced perylene core.
已经合成了一系列多态氧化还原活性架构，对其结构进行了表征，并研究了它们的光学和氧化还原性质。具体来说，将两个氧化还原活性的二茂铁或钴-二硫烯部分引入到苝-双酰亚胺的“海湾”区域。这些取代的苝-双酰亚胺物种中的三种已通过单晶 X 射线衍射进行了结构表征，证实了中心苝核心的扭曲性质。第一个取代的苝-双酰亚胺异构体对，N,N'-二-(正丁基)-1,7-二茂铁基-苝-3,4:9,10-四羧酸二酰亚胺（2）和 N,N'-二-(正丁基)-1,6-二茂铁基-苝-3,4:9,10-四羧酸二酰亚胺（3），通过单晶 X 射线衍射进行了结构表征，并进行了比较。钴-二硫烯取代的苝-双酰亚胺，N,N'-二-(正丁基)-1,7-二环戊二烯基-钴（II）-二硫烯基-苝-3,4:9,10-四羧酸二酰亚胺（4）的结构表征表明，苝核心的预期扭曲，并证实了钴二硫烯部分的烯-二硫醇酯几何形状。1-4 的循环伏安测量，结合光谱电化学和电子顺磁共振研究，其中 1 是 N,N'-二-(正丁基)-1,7-二乙炔基二茂铁基-苝-3,4:9,10-四羧酸二酰亚胺，揭示了两个预期的苝-双酰亚胺基还原。此外，对于二茂铁取代的化合物 1-3，仅观察到一个可逆的双电子氧化，其中只有很小程度的二茂铁基团之间的通信，在 1,6-异构体中，两个二茂铁基团连接到同一个萘基部分。在 4 的情况下，观察到与钴-二硫烯部分相关的两个可逆还原，证实了穿过还原苝核心的通信。
