Synergistic σ/π-Hole Interactions Directing Supramolecular Assembly: Tellurium···Platinum Chalcogen Bonding Enhanced by π-Stacking

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-11-25 DOI:10.1021/acs.cgd.4c0123610.1021/acs.cgd.4c01236

Anastasiya A. Busygina, Anastasiya A. Eliseeva, Anton V. Rozhkov, Daniil M. Ivanov, Rosa M. Gomila, Antonio Frontera, Nadezhda A. Bokach* and Vadim Yu. Kukushkin*,

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引用次数: 0

Abstract

This study investigates the synergistic effects of σ- and π-hole interactions in directing supramolecular assembly, focusing on unusual Te^II···Pt^II chalcogen bonding enhanced by π-stacking. Three novel cocrystals were synthesized and characterized, combining the dithiocarbamate complexes [Pt(ppy)(S₂CNC₆H₁₂)] and [Pt(ppy)(S₂CNC₄H₈)] (where ppyH = 2-phenylpyridine) with the tellurium(II)-based mixed σ/π-hole donors Te(C₅F₄N-4)₂ and Te(C₆F₄CF₃-4)₂. X-ray crystallography revealed a diverse array of noncovalent interactions, including two-center Te···Pt and three-center Te···(Pt,S) and Te···(Pt,C) chalcogen bonds, where the σ-Te^II-hole interacts directly with the d_z²-orbital of the positively charged platinum(II) ion. These unusual chalcogen bonds are significantly reinforced by π-stacking between the electron-deficient aromatic rings and platinum complex ligands. This combination of σ- and π-hole-based contacts leads to more robust and diverse supramolecular architectures compared to systems with isolated interactions. Theoretical calculations using QTAIM, NCIPlot, and NBO methods closely interrogated the interplay of these noncovalent forces highlighting the important role of electronic effects in controlling the balance between chalcogen bond and the π-stacking.

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协同σ/π-空穴作用指导超分子组装：π-Stacking增强碲···铂·硫键

本文研究了σ-和π-空穴相互作用在指导超分子组装中的协同作用，重点研究了π-堆叠增强的TeII···PtII硫键。将二硫代氨基甲酸酯配合物[Pt(ppy)(S2CNC6H12)]和[Pt(ppy)(S2CNC4H8)]（其中ppyH = 2-苯基吡啶）与碲（II）基混合σ/π孔给体Te(C5F4N-4)2和Te(C6F4CF3-4)2合成并表征了三种新型共晶。x射线晶体学显示了多种非共价相互作用，包括双中心Te··Pt和三中心Te···（Pt，S）和Te···（Pt，C）硫键，其中σ- teii空穴直接与带正电的铂（II）离子的dz2轨道相互作用。缺乏电子的芳香环和铂配合配体之间的π堆积明显加强了这些不寻常的硫键。与具有孤立相互作用的系统相比，这种基于σ-和π-空穴的接触组合导致了更健壮和多样化的超分子结构。利用QTAIM、NCIPlot和NBO方法进行的理论计算密切探讨了这些非共价力的相互作用，强调了电子效应在控制硫键和π堆积之间的平衡中的重要作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.