Control of Molecular Packing in Crystal and Electron Communication of Two Ferrocenyl Moieties across Chiral Isomannide or Isosorbide Bridge

CRYSTALS(2023)

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摘要
Intramolecular electronic communication between electrochemically active groups connected by a bridging moiety can be modified through small changes in the spatial disposition of the redox active moieties and/or by the nature of the central core. In this study, chiral bio-based compounds, namely isomannide and isosorbide, were employed as cheap and easy-to-functionalize chiral scaffolds to bridge two ferrocenyl electroactive moieties. The crystal structures of both bis-ferrocenyl diester complexes were studied and they showed that the chirality of the bridge results in an open or tight helical crystal packing. The electron communication between the two electroactive units in the mixed valent monocations was also investigated using electrochemistry (cyclic voltammetry and differential pulsed voltammetry), and spectroelectrochemistry in the UV-Vis NIR. A computational study through time-dependent DFT was also employed to gain greater insight into the results obtained.
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关键词
isohexide,ferrocene,electron communication,cyclic voltammetry,differential pulsed voltammetry,isomannide,isosorbide,spectroelectrochemistry,X-ray diffraction,crystal
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