Double Chalcogen Bonds: Crystal Engineering Stratagems via Diffraction and Multinuclear Solid-State Magnetic Resonance Spectroscopy
| Autor: | Vijith Kumar, David L. Bryce, Yijue Xu |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Chemistry Organic Chemistry Supramolecular chemistry chemistry.chemical_element General Chemistry Nuclear magnetic resonance spectroscopy 010402 general chemistry Crystal engineering 01 natural sciences Catalysis 0104 chemical sciences Chalcogen Crystallography Solid-state nuclear magnetic resonance Density functional theory Molecular orbital Tellurium |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany). 26(15) |
| ISSN: | 1521-3765 |
| Popis: | Group 16 chalcogens potentially provide Lewis-acidic σ-holes, which are able to form attractive supramolecular interactions with electron rich partners through chalcogen bonds. Here, a multifaceted experimental and computational study of a large series of novel chalcogen-bonded cocrystals, prepared using the principles of crystal engineering, is presented. Single-crystal X-ray diffraction studies reveal that dicyanoselenadiazole and dicyanotelluradiazole derivatives work as promising supramolecular synthons with the ability to form double chalcogen bonds with a wide range of electron donors including halides and oxygen- and nitrogen-containing heterocycles. Extensive 77 Se and 125 Te solid-state nuclear magnetic resonance spectroscopic investigations of cocrystals establish correlations between the NMR parameters of selenium and tellurium and the local chalcogen bonding geometry. The relationships between the electronic environment of the chalcogen bond and the 77 Se and 125 Te chemical shift tensors were elucidated through a natural localized molecular orbital density functional theory analysis. This systematic study of chalcogen-bond-based crystal engineering lays the foundations for the preparation of the various multicomponent systems and establishes solid-state NMR protocols to detect these interactions in powdered materials. |
| Databáze: | OpenAIRE |
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