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Synchrotron powder diffraction in a systematic study of 4'-[2-(tosylamino)benzylideneamino]-2,3benzo-15-crown-5 complexesстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Dorokhov Andrey V., Chernyshov Dmitrii Yu, Burlov Anatolii S., Garnovskii Alexandr D., Ivanova Irina S., Pyatova Elena N., Tsivadze Aslan Yu, Aslanov Leonid A., Chernyshev Vladimir V.
- Журнал: Acta Crystallographica Section B: Structural Science
- Том: 63
- Год издания: 2007
- Издательство: Blackwell Publishing Inc.
- Местоположение издательства: United Kingdom
- Первая страница: 402
- Последняя страница: 410
- DOI: 10.1107/S0108768107003898
- Аннотация: The crystal structures of two compounds, CuL2 and LiNCS center dot HL [HL = 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5], have been determined from synchrotron powder diffraction data. Both compounds crystallize in the monoclinic space group P2(1)/c and with one molecule in the asymmetric unit. In CuL2 the four N atoms of two bidentate L ligands coordinate the Cu-II ion in a distorted tetrahedral geometry with Cu-N distances of 1.98 (5)-2.05 (5) angstrom, while two O atoms from two sulfoxide groups complete the distorted octahedral Cu coordination [Cu-O 2.64 (4), 2.74 (4) angstrom]. In LiNCS center dot HL, lithium is coordinated by all five ether O atoms with Li-O distances of 2.03 (3)-2.50 (3) angstrom and an N atom from the thiocyanate moiety [Li-N 1.98 (3) angstrom] in a distorted pentagonal pyramidal geometry. Preliminary potentiometric selectivity measurements for ion-selective electrodes (ISEs) based on CuL2 and ZnL2 demonstrated significant differences in their selectivity. In order to find a possible reason for this, theoretical calculations at the DFT (B3LYP) level were performed. These calculations used the crystal structures of CuL2, LiNCS center dot HL, ZnL2 and HL as input geometries for the minimum energy optimization in vacuo. The results indicate that in ML2 complexes (M = Cu, Zn) the electronic structure of the metal ion determines the spatial orientation of benzo-15-crown-5 macrocycles, and their different orientation in CuL2 and ZnL2 results in different potentiometric selectivities of ISEs based on these compounds.
- Добавил в систему: Чернышев Владимир Васильевич