Structural versatility of the quasi-aromatic Möbius type zinc(II)-pseudohalide complexes – experimental and theoretical investigations

Mariusz P. Mitoraj; Farhad Akbari Afkhami; Ghodrat Mahmoudi; Ali Akbar Khandar; Atash V. Gurbanov; Fedor I. Zubkov; Rory Waterman; Maria G. Babashkina; Dariusz W. Szczepanik; Himanshu S. Jena; Damir A. Safin

doi:10.1039/C9RA05276C

Structural versatility of the quasi-aromatic Möbius type zinc(ii)-pseudohalide complexes – experimental and theoretical investigations†

Mariusz P. Mitoraj,

*^a Farhad Akbari Afkhami,

^b Ghodrat Mahmoudi,

*^c Ali Akbar Khandar,^b Atash V. Gurbanov,

^de Fedor I. Zubkov,

^f Rory Waterman,

^g Maria G. Babashkina,^h Dariusz W. Szczepanik,

^a Himanshu S. Jena

ⁱ and Damir A. Safin

*^h

Author affiliations

* Corresponding authors

^a Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Cracow, Poland
E-mail: mitoraj@chemia.uj.edu.pl

^b Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

^c Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
E-mail: mahmoudi_ghodrat@yahoo.co.uk

^d Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Baku, Azerbaijan

^e Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisboa, Portugal

^f Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, Russian Federation

^g Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405, USA

^h Institute of Chemistry, University of Tyumen, Perekopskaya Str. 15a, 625003 Tyumen, Russian Federation
E-mail: damir.a.safin@gmail.com, d.a.safin@utmn.ru

ⁱ COMOC, Department of Chemistry, Ghent University, Krijgslaan 281-S3B, Ghent-9000, Belgium

Abstract

In this contribution we report for the first time fabrication, isolation, structural and theoretical characterization of the quasi-aromatic Möbius complexes [Zn(NCS)₂L^I] (1), [Zn₂(μ_1,1-N₃)₂(L^I)₂][ZnCl₃(MeOH)]₂·6MeOH (2) and [Zn(NCS)L^II]₂[Zn(NCS)₄]·MeOH (3), constructed from 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (L^I) or benzilbis(acetylpyridin-2-yl)methylidenehydrazone (L^II), 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 Zn^II atom chelated by one tetradentate twisted ligand L^I 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.

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Structural versatility of the quasi-aromatic Möbius type zinc(ii)-pseudohalide complexes – experimental and theoretical investigations†

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Structural versatility of the quasi-aromatic Möbius type zinc(II)-pseudohalide complexes – experimental and theoretical investigations

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