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Cation-Stacking Approach Enabling Interconversion between Bis(xanthylium) and its Reduced Species
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DOI：10.1002/chem.202401683.png)
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Abstract
En 中文
Cyclophane-type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X-ray and UV/Vis measurements revealed that the cyclophane-type dications adopt a stacking structure in both the crystal and solution. Due to the intramolecular interaction caused by pi-pi stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two-stage one-electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation-stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open-shell characters. For the newly designed cyclophane-type dications, the xanthylium units facing each other exert attractive rather than repulsive effects, even though there is electrostatic repulsion between cation units. Due to an intramolecular interaction caused by pi-pi stacking, not only the dications but also their reduced species can be stabilized. Thus, stepwise redox interconversion was achieved via radical cation species. image
Keywords:
Cations
Cyclophane
Electrochromism
Radicals
Redox systems
Journal
C
IF:
3.7
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3.9W
Citations:
9.6W