Issue 26, 2018

The intramolecular hydrogen bonded–halogen bond: a new strategy for preorganization and enhanced binding

Abstract

Natural and synthetic molecules use weak noncovalent forces to preorganize structure and enable remarkable function. Herein, we introduce the intramolecular hydrogen bonded–halogen bond (HB–XB) as a novel method to preorganize halogen bonding (XBing) molecules, while generating a polarization-enhanced XB. Positioning a fluoroaniline between two iodopyridinium XB donors engendered intramolecular hydrogen bonding (HBing) to the electron-rich belt of both XB donors. NMR solution studies established the efficacy of the HB-XB. The receptor with HB–XBs (G2XB) displayed a nearly 9-fold increase in halide binding over control receptors. Gas-phase density functional theory conformational analysis indicated that the amine stabilizes the bidentate conformation. Furthermore, gas-phase interaction energies showed that the bidentate HB–XBs of G2XBme2+ are more than 3.2 kcal mol−1 stronger than the XBs in a control without the intramolecular HB. Additionally, crystal structures confirm that HB–XBs form tighter contacts with I and Br and produce receptors that are more planar. Collectively the results establish the intramolecular HB–XB as a tractable strategy to preorganize XB molecules and regulate XB strength.

Graphical abstract: The intramolecular hydrogen bonded–halogen bond: a new strategy for preorganization and enhanced binding

Associated articles

Supplementary files

Article information

Article type
Edge Article
Submitted
01 5 2018
Accepted
13 6 2018
First published
21 6 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 5828-5836

The intramolecular hydrogen bonded–halogen bond: a new strategy for preorganization and enhanced binding

A. M. S. Riel, D. A. Decato, J. Sun, C. J. Massena, M. J. Jessop and O. B. Berryman, Chem. Sci., 2018, 9, 5828 DOI: 10.1039/C8SC01973H

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