Stable Aromatic Dianion in Water

Abstract

Perylene diimide (PDI) bearing polyethylene glycol substituents at the imide positions was reduced in water with sodium dithionite to produce an aromatic dianion. The latter is stable for months in deoxygenated aqueous solutions, in contrast to all known aromatic dianions which readily react with water. Such stability is due to extensive electron delocalization and the aromatic character of the dianion, as evidenced by spectroscopic and theoretical studies. The dianion reacts with oxygen to restore the parent neutral compound, which can be reduced again in an inert atmosphere with sodium dithionite to give the dianion. Such reversible charging renders PDIs useful for controlled electron storage and release in aqueous media. Simple preparation of the dianion, reversible charging, high photoredox power, and stability in water can lead to development of new photofunctional and electron transfer systems in the aqueous phase.

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

“…Thus, the electrochemistry is strongly influenced by the aggregation modes. [10] The sharp peak in the case of 1 P is consistent with uniform structure and stronger electronic coupling resulting from extensive overlap of the aromatic moieties. Two distinct reduction peaks for 1 G point to a lesser degree of coupling and greater similarity to the individual molecules of 1.…”

Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air‐Insensitive Electron Acceptors for Artificial Photosynthesis

“…[56] Likewise, serious electron mobility degradation was observed in PDI and fullerene derivatives for OFETs upon exposure to air. [59–61] This is a result of electron trapping by absorbed O 2 and water.…”

Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO)3 using red and near-infrared light

“…13 When stored under inert atmosphere, these chromophores are stable in organic or even aqueous solution. 14 A similar strategy, in which a reduced chromophore is used to sensitize a Re(bpy)(CO) 3 center, has been reported very recently by Neumann and co-workers in a system incorporating a reduced polyoxometalate as a long-wavelength-absorbing chromophore. 15 This method, in which a highly reducing chromophore is easily generated using chemical or electrochemical means and subsequently used to drive a highly endothermic electron transfer reaction, is applicable not only to the study of carbon-dioxide reduction, but could also be employed to facilitate other transformations such as photoelectrocatalytic N 2 reduction or photoredox reactions involving electron-rich organic substrates that are not easily reduced using typical photoredox chromophores.…”