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

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: 2.44e in 3, 3.14e in 2 and 3.44e 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. © 2019 The Royal Society of Chemistry.

Mitoraj M.P.1 , Afkhami F.A.2 , Mahmoudi G. 3 , Khandar A.A.2 , Gurbanov A.V. 4, 5 , Zubkov F.I. 6 , Waterman R.7 , Babashkina M.G.8 , Szczepanik D.W.1 , Jena H.S.9 , Safin D.A.8
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  • 1 Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Cracow, 30-387, Poland
  • 2 Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, 51666-16471, Iran
  • 3 Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
  • 4 Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Baku, AZ1148, Azerbaijan
  • 5 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1049-001, Lisboa, Portugal
  • 6 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
  • 7 Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405, United States
  • 8 Institute of Chemistry, University of Tyumen, Perekopskaya Str. 15a, Tyumen, 625003, Russian Federation
  • 9 COMOC, Department of Chemistry, Ghent University, Krijgslaan 281-S3B, Ghent, 9000, Belgium
Ключевые слова
Aromatic compounds; Aromatization; Cadmium compounds; Chlorine compounds; Ligands; Single crystals; Sodium Azide; Zinc chloride; Electrostatic stabilization; London dispersion forces; Mononuclear structures; Non-covalent interaction; Organic ligands; Pseudohalide complexes; Single crystal x-ray diffraction; Theoretical investigations; Crystal atomic structure
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