Dataset Information

Do CH-Anion and Anion-? Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

ABSTRACT: Selective tuning of arylethynyl urea scaffolds for anionic guests requires an understanding of preferred binding motifs of the host-guest interaction. To investigate the binding preference of receptors without a pre-organized binding pocket, two electron-deficient phenylacetylene receptors with a single urea moiety have been prepared and were found to bind halides as 2:1 host-guest complexes that feature key CH-anion or anion-? interactions. These supporting interactions also appear to influence the mechanism of the 2:1 binding event.

SUBMITTER: Eytel LM

PROVIDER: S-EPMC5560113 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Publications

Do CH-Anion and Anion-π Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

Eytel Lisa M LM Gilbert Annie K AK Görner Paul P Zakharov Lev N LN Johnson Darren W DW Haley Michael M MM

Chemistry (Weinheim an der Bergstrasse, Germany) 20170306 17

Selective tuning of arylethynyl urea scaffolds for anionic guests requires an understanding of preferred binding motifs of the host-guest interaction. To investigate the binding preference of receptors without a pre-organized binding pocket, two electron-deficient phenylacetylene receptors with a single urea moiety have been prepared and were found to bind halides as 2:1 host-guest complexes that feature key CH-anion or anion-π interactions. These supporting interactions also appear to influence ...[more]

PMID: 28198117

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Project description: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.

Dataset Information

Do CH-Anion and Anion-? Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

Publications

Do CH-Anion and Anion-π Interactions Alter the Mechanism of 2:1 Host-Guest Complexation in Arylethynyl Monourea Anion Receptors?

Similar Datasets

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