Water-Stable, Eight-electron Acceptor Drives Anion⋅⋅⋅Water Assisted Tunable Ionic Self-Assembly and Proton Conduction.

Autor: Shukla J; Supramolecular and Material Chemistry Lab, School of Physical Sciences, Jawaharlal Nehru University, Delhi, 110067, India., Bera SP; Department Department of Chemistry, IISER Bhopal, Bhopal, 462066, India., Ajayakumar MR; Supramolecular and Material Chemistry Lab, School of Physical Sciences, Jawaharlal Nehru University, Delhi, 110067, India., Konar S; Department Department of Chemistry, IISER Bhopal, Bhopal, 462066, India., Mukhopadhyay P; Supramolecular and Material Chemistry Lab, School of Physical Sciences, Jawaharlal Nehru University, Delhi, 110067, India.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Sep 19; Vol. 30 (53), pp. e202401334. Date of Electronic Publication: 2024 Sep 03.
DOI: 10.1002/chem.202401334
Abstrakt: 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 +0.05 V and -1.12 V. The supramolecular interactions and the ensuing ionic framework are tunable based on the three anions, e. g., Cl - , Br - and PF 6 - , 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 -3  S cm -1 . In contrast, the ionic assembly formed by the lipophilic PF 6 - 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.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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