A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems.
A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems.
复制标题
DOI：
10.1107/s2052252515010854
复制
发表时间：
2015-09-01
期刊：
影响因子：
3.9
通讯作者：
Desper J
中科院分区：
文献类型：
--
作者：
Aakeröy CB;Spartz CL;Dembowski S;Dwyre S;Desper J
对共晶体中氢键和卤素键的结构研究有助于阐明在实际的超分子合成中它们之间的竞争和平衡。随着卤键在超分子合成和材料化学中的流行，有必要更仔细地研究这种相互作用如何与氢键竞争或互补，无论何时两者都存在于同一系统中。由于氢键和卤键有几个共同的基本特征，通常很难预测哪一个将是超分子体系中的主要相互作用，特别是当它们具有可比的强度和几何要求时。为了解决这一挑战，一系列的分子含有氢键和卤素键供体共结晶与各种单调的，ditopic对称和ditopic不对称受体分子。每个反应的结果进行了检查，使用红外光谱，并在可能的情况下，单晶X-射线衍射。获得了24种晶体结构，随后进行了分析，并对计算的分子静电势值的背景下，合理化的竞争氢键和卤素键供体的合成子偏好。它已被证明，易于访问的静电势可以提供有用的实用指南，预测这些共晶中最有可能的初级双光子，只要电位差被适当加权。
An extensive structural study on hydrogen and halogen bonding in co-crystals has helped clarify the competition and balance between them in a practical supramolecular synthesis. As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.