| Autor: |
Strelnikova IV; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru.; Kazan Federal University, Kremlevskaya 18 str, Kazan 420008, Russian Federation., Ovsyannikov AS; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru., Gubaidullin AT; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru., Agarkov AS; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru., Kleshnina SR; Kazan Federal University, Kremlevskaya 18 str, Kazan 420008, Russian Federation., Iova AA; Kazan Federal University, Kremlevskaya 18 str, Kazan 420008, Russian Federation., Furer VL; Kazan State Architect and Civil Engineering University, 1 Zelenaya Str., 420043 Kazan, Russian Federation., Vandyukov AE; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru., Solovieva SE; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova 8 str, Kazan 420088, Russian Federation. osaalex2007@rambler.ru., Antipin IS; Kazan Federal University, Kremlevskaya 18 str, Kazan 420008, Russian Federation. |
| Abstrakt: |
The rational design of organic ligands with the aim to control their binding abilities towards different metal ions can be considered as one of the key concepts in supramolecular coordination chemistry. Regarding the macrocyclic compounds of thiacalix[4]arene family, this can be achieved via the targeted modulation of macrocyclic platform rigidity as well as the proper choice of appended binding sites. Four macrocyclic salen-type ligands based on lower rim disubstituted thiacalix[4]arene derivatives, adopted in a cone conformation, bearing highly coordinating iminophenolic or catecholic groups and two -CH 2 - moieties as spacers but presenting different abilities to form H-bonds, were chosen to elucidate the interplay between the conformational flexibility of the macrocyclic ligands, propensity to participate in the intermolecular H-bonding and the extraction ability of 3d-metal cations. X-ray diffraction analysis, theoretical DFT calculations, IR and Raman spectroscopies, and dynamic light scattering (DLS) studies performed in combination with liquid-liquid metal extraction study revealed that compounds 4, and 6, based on a thiacalix[4]arene macrocyclic platform, display a higher extraction ability towards all studied 3d-metal ions, caused by enhanced conformational flexibility. This is in good accordance with the ability of 6 to form H-bonded supramolecular assemblies in solution and crystalline phases due to recognition between the catecholic moieties. |
