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Updated: Dec 9, 2025

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen
1The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Abstract:
It is found by experiment that the cationic halogen bond donors (cationic iodoimidazolium compounds) can activate the Ritter-type solvolysis of benzhydryl bromide, while the cationic hydrogen bond donors (cationic imidazolium compounds) could not. To understand the activation mechanism, various noncovalent interactions between benzhydryl bromide and a series of activators in solution, including halogen bond, hydrogen bond, lone pair···π/π+, and C-H···π/π+, were explored theoretically. Our study revealed that the activation difference can be contributed by the variation of the noncovalent interactions. For halogen bond donors, the successful activation is attributed by halogen bond and lone pair···π. The halogen bonds mainly provide the stabilization energy of the ion-pair complex with the help of lone pair···π. For hydrogen-bond donors, the contribution of the hydrogen bond is unable to compensate the like-charge repulsion arising from the generation of the carbocation, leading to the unsuccessful activation. In general, lone pair···π makes a difference.
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