硫属原子大小决定苯-1,3,5-三酰胺聚合物的稳定性：被忽视的几何适应性在增强氢键中的作用。
Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding.
作者信息
Nieuwland Celine, Lekanne Deprez Siebe, de Vries Claris, Fonseca Guerra Célia
机构信息
Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
出版信息
Chemistry. 2023 Jun 19;29(34):e202300850. doi: 10.1002/chem.202300850. Epub 2023 May 2.
Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.
我们的量子化学分析阐明了在苯-1,3,5-三羧酸酰胺（OBTAs）的酰胺键中用较大的硫族元素 S 和 Se 替代 O，如何增强分子间相互作用，从而提高所得氢键超分子聚合物的稳定性，原因有两个：i）SBTA 和 SeBTA 单体具有更好的自组装几何形状；ii）除了增强分散相互作用外，还诱导更强的共价（氢键）相互作用。此外，还表明苯-1,3,5-三酰胺（BTA）自组装中的协同作用是由氢键中的共价性引起的σ-电子系统中的电荷分离引起的。
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