Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.
Drug Discovery and Design Center, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203, China.
J Phys Chem A. 2021 May 20;125(19):4173-4183. doi: 10.1021/acs.jpca.1c03244. Epub 2021 May 6.
Noncovalent chalcogen-chalcogen interactions are being actively investigated from both crystallographic and theoretical viewpoints in recent years. According to our search of the Cambridge Structural Database (CSD), a huge number of crystal structures containing triangular Ch synthons were extracted. On the basis of the results of the CSD survey, a series of trimeric complexes of organic divalent chalcogen molecules were selected to model such interaction motifs. Similar to that in conventional chalcogen bonds, triangular interchalcogen interactions become gradually stronger along the sequence of Ch = S, Se, Te. Particularly, hydrogen bonds between the chalcogen centers and the H atoms in the substituents occur, which play a significant role in stabilizing the Ch motifs in the trimers. Through multibody energy calculations, the complexes under study exhibit no or only weak cooperativity. Finally, the differences between the Ch interaction motifs and the well-studied windmill X bonding (X means halogen and this is halogen bond) patterns were elucidated.
近年来，从晶体学和理论观点两个方面，非共价的硫属元素-硫属元素相互作用受到了广泛的研究。根据我们对剑桥结构数据库（CSD）的搜索，提取了大量包含三角 Ch 桥联单元的晶体结构。基于 CSD 调查的结果，选择了一系列有机二价硫属元素分子的三聚体复合物来模拟这种相互作用模式。与传统的硫属元素键类似，三角型的内硫属元素相互作用沿着 Ch = S、Se、Te 的顺序逐渐增强。特别地，硫属元素中心与取代基中 H 原子之间发生氢键，这在稳定三聚体中的 Ch 模式中起着重要作用。通过多体能量计算，所研究的配合物没有或只有较弱的协同性。最后，阐明了 Ch 相互作用模式与研究充分的风车 X 键（X 表示卤素，这是卤素键）模式之间的差异。
