مشخصات پژوهش

صفحه نخست /Structural versatility of the ...
عنوان Structural versatility of the quasi-aromatic Möbius type zinc(II)-pseudohalide complexes – experimental and theoretical investigations
نوع پژوهش مقاله چاپ‌شده در مجلات علمی
کلیدواژه‌ها long-range electrostatic stabilization
چکیده In this contribution we report for the first time fabrication, isolation, structural and theoretical characterization of the quasi-aromatic Möbius complexes [Zn(NCS)2LI] (1), [Zn2(μ1,1-N3)2(LI)2][ZnCl3(MeOH)]2·6MeOH (2) and [Zn(NCS)LII]2[Zn(NCS)4]·MeOH (3), constructed from 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (LI) or benzilbis(acetylpyridin-2-yl)methylidenehydrazone (LII), respectively, and ZnCl2 mixed with NH4NCS or NaN3. Structures 1–3 are dictated by both the bulkiness of the organic ligand and the nature of the inorganic counter ion. As evidenced from single crystal X-ray diffraction data species 1 has a neutral discrete heteroleptic mononuclear structure, whereas, complexes 2 and 3 exhibit a salt-like structure. Each structure contains a ZnII atom chelated by one tetradentate twisted ligand LI creating the unusual Möbius type topology. Theoretical investigations based on the EDDB method allowed us to determine that it constitutes the quasi-aromatic Möbius motif where a metal only induces the π-delocalization solely within the ligand part: 2.44|e| in 3, 3.14|e| in 2 and 3.44|e| in 1. It is found, that the degree of quasi-aromatic π-delocalization in the case of zinc species is significantly weaker (by ∼50%) than the corresponding estimations for cadmium systems – it is associated with the Zn–N bonds being more polar than the related Cd–N connections. The ETS-NOCV showed, that the monomers in 1 are bonded primarily through London dispersion forces, whereas long-range electrostatic stabilization is crucial in 2 and 3. A number of non-covalent interactions are additionally identified in the lattices of 1–3.
پژوهشگران دمیر سفین (نفر ششم به بعد)، هیمانشو سخار (نفر ششم به بعد)، دارییسز اسزیپلنیک (نفر ششم به بعد)، ماریا باباشینکا (نفر ششم به بعد)، روری واترمن (نفر ششم به بعد)، فدور زوبکو (نفر ششم به بعد)، آتش قربانو (نفر پنجم)، علی اکبر خاندار (نفر چهارم)، قدرت محمودی (نفر سوم)، فرهاد اکبری افخمی (نفر دوم)، مارسیز میتوراج (نفر اول)