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“Anti-Electrostatic” Halogen Bonding

preprint
submitted on 28.02.2020, 16:55 and posted on 02.03.2020, 13:04 by Jana Holthoff, Elric Engelage, Robert Weiss, Stefan Huber
Halogen bonding (XB) is often described as being driven predominantly by electrostatics, and thus adducts between anionic XB donors (halogen-based Lewis acids) and anions seem counter­intuitive. Such “anti-electrostatic” XBs have been predicted theoretically, but there are currently no experimental examples based on organic XB donors. Herein, we report the synthesis of two negatively charged organoiodine derivatives, which were subsequently investigated towards their ability to form “anti-electrostatic” XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self-association of the anionic XB donors was observed in solid-state structures, resulting in dimers, trimers and infinite chains. In addition, co-crystals with halides were obtained which featured XB adducts between two or even three anions. The bond-lengths of all observed interactions are 14-21% shorter than sum of the van-der-Waals radii.

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in Angewandte Chemie International Edition

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Funding

German Research Foundation

Studienstiftung des Deutschen Volkes

History

Email Address of Submitting Author

stefan.m.huber@rub.de

Institution

Ruhr-University Bochum

Country

Germany

ORCID For Submitting Author

0000-0002-4125-159X

Declaration of Conflict of Interest

No conflict of interest

Exports

Read the published paper

in Angewandte Chemie International Edition

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Exports