Document Type

Article

Publication Date

1-3-2018

Publication Title

Crystal Growth and Design

Volume

18

Issue

1

First Page

513

Last Page

520

Abstract

Halogen bonding provides a useful complement to hydrogen bonding and metal-coordination as a tool for organizing supramolecular systems. Resorcinarenes, tetrameric bowl-shaped cavitands, have been previously shown to function as efficient scaffolds for generating dimeric capsules in both solution and solid-phase, and complicated one-, two-, and three-dimensional frameworks in the solid phase. Tetrahaloethynyl resorcinarenes (bromide and iodide) position the halogen atoms in a very promising "crown-like" orientation for acting as organizing halogen-bond donors to help build capsules and higher-order networks. Symmetric divalent halogen bond acceptors including bipyridines, 1,4-dioxane, and 1,4-diazabicyclo[2.2.2]octane are very promising halogen bond accepting partners for creating these systems. This report describes the complex structures arising from combining these various systems including self-included dimers, herringbone-packed architectures enclosing medium (186 Å3) cavities, and a very intriguing bamboo-like one-dimensional rod with large (683 Å3) cavities between adjacent dimeric units. These various structures, all organized through host-host, host-acceptor, and host-solvent interactions highlight the emergent complexity of these types of complexes. As halogen bonds are weaker than hydrogen-bonds, the resulting architectures are harder to predict, and these results provide additional insight into the parameters requiring consideration when designing crystalline supramolecular systems using halogen-bonds as the core organizing principle.

DOI

10.1021/acs.cgd.7b01517

ISSN

15287483

E-ISSN

15287505

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