通过卤素键组装的基于三碘化物的椅状铜配合物

Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding.

作者信息

Kinzhalov Mikhail A, Kinzhalova Ekaterina I, Karnoukhova Valentina A, Ananyev Ivan V, Gomila Rosa M, Frontera Antonio, Kukushkin Vadim Yu, Bokach Nadezhda A

机构信息

Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.

Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 30 Lenin Av., Tomsk 634050, Russian Federation.

出版信息

Inorg Chem. 2024 Jan 8;63(1):191-202. doi: 10.1021/acs.inorgchem.3c02990. Epub 2023 Dec 18.

DOI:10.1021/acs.inorgchem.3c02990

PMID:38108293

Abstract

Cocrystallization of the dimeric [Cu(μ-I)(CNXyl)] (Xyl = 2,6-MeCH, ) and polymeric -[Cu(μ-I)(CNCH-2-Cl-6-Me)] () complexes with I at different molar ratios between the reactants resulted in a series of (RNC)CuI-based crystal polyiodides formed along with gradual accumulation of iodine, namely the cocrystals [·I]·[Cu(μ-I)(CNXyl)] followed by the generation of [Cu(μ-I)(CNXyl)]·2I (·2I) or [Cu(μ-I)(CNCH-2-Cl-6-Me)] and then [Cu(μ-I)(CNCH-2-Cl-6-Me)]·/I. The polyiodide ·2I exhibits a novel supramolecular motif─a purely inorganic halogen-bonded Cu(μ-I) core in the chair conformation. The X-ray structure of ·2I featuring I···I contacts was analyzed by a set of theoretical methods and attributed to moderately strong halogen bonding (from -3.2 to -3.9 kcal/mol); these interactions determine the supramolecular architecture of ·2I.

摘要

二聚体[Cu(μ-I)(CNXyl)]（Xyl = 2,6-Me₂C₆H₃）和聚合物 -[Cu(μ-I)(CNCH₂Cl-6-Me)]与碘以不同摩尔比进行共结晶，反应物之间会生成一系列基于(RNC)CuI的晶体多碘化物，并伴有碘的逐渐积累，即共晶体[·I]·[Cu(μ-I)(CNXyl)]，随后生成[Cu(μ-I)(CNXyl)]·2I（·2I）或[Cu(μ-I)(CNCH₂Cl-6-Me)]，然后是[Cu(μ-I)(CNCH₂Cl-6-Me)]·/I。多碘化物·2I呈现出一种新颖的超分子结构基元——椅式构象的纯无机卤素键合Cu(μ-I)核心。通过一组理论方法分析了具有I···I接触的·2I的X射线结构，并将其归因于中等强度的卤素键（-3.2至-3.9 kcal/mol）；这些相互作用决定了·2I的超分子结构。