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Molecular recognition of pyrazine N,N′-dioxide using aryl extended calix[4]pyrroles

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Abstract

Calix[4]pyrrole (C4P)-based systems have been extensively explored as binding agents for anions and ion pairs. However, their capacity to act as molecular containers for neutral species remains underexplored. We report here the molecular recognition of pyrazine N,N′-dioxide (PZDO) using a series of aryl extended C4Ps including three α,α-diaryl substituted C4Ps (receptors 1–3), an α,β-diaryl substituted C4P (receptor 4) and an α,α,α,α-tetraaryl substituted C4P (receptor 5). Single crystal structural analyses of the 2 : 1 host–guest complexes between receptors 1–3 and PZDO revealed that the C4P subunits exist in an unusual partial cone conformation and that the PZDO guest is held within electron-rich cavities formed by the lower rims of the individual C4P macrocycle. In contrast, receptor 5 was seen to adopt the cone conformation in the solid state, allowing one PZDO molecule to be accommodated inside the upper-rim cavity. Evidence for guest-directed self-assembly is also seen in the solid state. Evidence for C4P–PZDO interactions in CD3CN/CD3OD solution came from 1H NMR spectroscopic titrations. Electrostatic potential maps created by means of density functional theory calculations were constructed. Density functional theory calculations were also performed to analyse the energetics of various limiting binding modes. On the basis of these studies, it is inferred that interactions between the ‘two-wall’ C4P derivatives (i.e. receptors 1–4) and PZDO involve a complex binding mode that differs from what has been seen in previous host–guest complexes formed between C4Ps and N-oxides. The present study thus paves the way for the further design of C4P-based receptors with novel recognition features.

Graphical abstract: Molecular recognition of pyrazine N,N′-dioxide using aryl extended calix[4]pyrroles

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Supplementary files

Article information


Submitted
11 Mar 2020
Accepted
19 Apr 2020
First published
20 Apr 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Molecular recognition of pyrazine N,N′-dioxide using aryl extended calix[4]pyrroles

C. Guo, H. Wang, V. M. Lynch, X. Ji, Z. A. Page and J. L. Sessler, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01496F

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