Water-Stable, Eight-electron Acceptor Drives Anionâ
â
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Water Assisted Tunable Ionic Self-Assembly and Proton Conduction.
Chemistry
; 30(53): e202401334, 2024 Sep 19.
Article
en En
| MEDLINE
| ID: mdl-38923656
ABSTRACT
Organic π-scaffolds are being envisaged for new-age electron- and ion-responsive materials that can accumulate electrons as well as transport proton. However, such systems are extremely rare as electron-deficient scaffolds are unstable in aqueous solution. Here we detail the synthesis of a water-stable core-naphthalenediimide-nitrobenzyl-viologen based tetra-cation, which accumulates up to eight-electrons within an exceptionally narrow potential window of +0.05â
V and -1.12â
V. The supramolecular interactions and the ensuing ionic framework are tunable based on the three anions, e. g., Cl-, Br- and PF6 -, that are investigated in this work. The ionic framework is formed and supported by a range of H-bonds, in which, the nitro benzyl groups act as pillars connecting the 1D water-tapes and the halide anions. The water molecules are hydrogen-bonded with the halide anions and bestow a facile pathway for the proton conduction, with proton conductivity up to 3.19×10-3â
S cm-1. In contrast, the ionic assembly formed by the lipophilic PF6 - anions do not host the water tapes and consequently the proton conductivity is found to be four orders of magnitude lower. This is a unique example, whereby proton conductivity is realized and is tunable within a highly electron-deficient, eight-electron acceptor, water-stable ionic supramolecular system.
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2024
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Article