Issue 59, 2020

Resonance-assisted/impaired anion–π interaction: towards the design of novel anion receptors

Abstract

Substituents alter the electron density distribution in benzene in various ways, depending on their electron withdrawing and donating capabilities, as summarized by the empirical Hammett equation. The change of the π electron density distribution subsequently impacts the interaction of substituted benzenes or other cyclic conjugated rings with anions. Currently the design and synthesis of conjugated cyclic receptors capable of binding anions is an active field due to their applications in the sensing and removal of environmental contaminants and molecular recognition. By using the block-localized wavefunction (BLW) method, which is a variant of ab initio valence bond (VB) theory and can derive the reference resonance-free state self-consistently, we quantified the resonance-assisted (RA) or resonance-impaired (RI) phenomena in anion–π interactions from both structural and energetic perspectives. The frozen interaction, in which the electrostatic attraction is involved, has been shown to be the governing factor for the RA or RI interactions with anions. Energy analyses based on the empirical point charge (EPC) model indicated that the anion–π interactions can be simplified as the attraction between a negative point charge (anion) and a group of local dipoles, affected by the enriched or diminished π-cloud due to the resonance between the substituents and the conjugated ring. Hence, two strategies for the design of novel anion receptors can be envisioned. One is the enhancement of the magnitudes and/or numbers of local dipoles (polarized σ bonds), and the other is the reduction of π electron density in conjugated rings. For cases with the RI characteristics, “curved” aromatic molecules are preferred to be anion receptors. Indeed, extremely strong binding was found in complexes formed with fluorinated corannulene (F-CDD) and fluorinated [5]cycloparaphenylene (F-[5]CPP). Inspired by the RA phenomenon, complexes of p-, o- and m-benzoquinones with halides were revisited.

Graphical abstract: Resonance-assisted/impaired anion–π interaction: towards the design of novel anion receptors

Supplementary files

Article information

Article type
Paper
Submitted
04 Aug 2020
Accepted
23 Sep 2020
First published
01 Oct 2020
This article is Open Access
Creative Commons BY license

RSC Adv., 2020,10, 36181-36191

Resonance-assisted/impaired anion–π interaction: towards the design of novel anion receptors

J. Du, C. Wang, S. Yin, W. Wang and Y. Mo, RSC Adv., 2020, 10, 36181 DOI: 10.1039/D0RA07877H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements