Chemisorptive Synthesis, Self-Assembly of Complicated 2D and 3D Supramolecular Architectures (Role of Hydrogen Bonds and
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isorptive Synthesis, Self-Assembly of Complicated 2D and 3D Supramolecular Architectures (Role of Hydrogen Bonds and Secondary Interactions Au···S and S···Cl), and Thermal Behavior of Pseudo-Polymeric Gold(III)–Mercury(II) Dibutyldithiocarbamato-Chlorido Complexes A. V. Ivanova, *, O. V. Losevaa, and T. A. Rodinaa aInstitute
of Geology and Nature Management, Far East Branch, Russian Academy of Sciences, Blagoveshchensk, Russia *e-mail: [email protected] Received November 29, 2019; revised December 8, 2019; accepted December 25, 2019
Abstract—The interaction of mercury(II) dibutyl dithiocarbamate (BuDtc) with [AuCl4]− anions in 2 M HCl was studied. The heterogeneous reaction of chemisorption binding of gold(III) from the solution leads to heteronuclear Au(III)–Hg(II) pseudo-polymeric complexes of the ionic type: ([Au{S2CN(C4H9)2}2]2[Hg2Cl6])n (I) and ([(C4H9)2NH2]0.5[Au{S2CN(C4H9)2}2]1.5[Hg2Cl6])n (II), whose crystal and supramolecular structures were determined by X-ray diffraction analysis (CIF files CCDC nos. 1965151 (I) and 1965152 (II)). The cationic part of each compound is represented by two structurally nonequivalent complex ions [Au{S2CN(C4H9)2}2]+ (A and B) being conformers. The structure of compound II additionally contains the dibutylammonium cation. In both cases, binuclear [Hg2Cl6]2– is a counterion (centrosymmetric in the structure of compound I and noncentrosymmetric in the structure of compound II). Owing to the secondary interactions Au···S and S···Cl (as well as hydrogen bonds N–H···Cl in compound II), all ionic structural units participate in the construction of pseudo-polymeric cationic and cation-anionic chains, which are combined into a complicatedly organized 2D supramolecular network (in I) or 3D framework (in II). The thermal behavior of compounds I and II was studied by simultaneous thermal analysis. The thermolysis of the complexes is accompanied by the quantitative regeneration of bound gold, liberation of HgCl2, and partial transformation of the latter into HgS. Keywords: mercury(II) dialkyl dithiocarbamates, chemisorption activity, double gold(III)–mercury(II) complexes, supramolecular self-assembly, secondary bonds Au⋅⋅⋅S and S⋅⋅⋅Cl, 13С CP-MAS NMR, thermal behavior DOI: 10.1134/S107032842009002X
INTRODUCTION The coordination compounds of mercury(II) with chelate ligands are interesting as a basis for photoluminescent and electroluminescent materials [1, 2] and also find use in medicine and agriculture owing to their fungicidal and antibacterial activity [3]. Mercury(II) dithiocarbamates are promising precursors for the production of film and nanosized mercury sulfides with luminescence and semiconductor properties, which are widely used in manufacturing ultrasonic and photoelectrical converters, image sensors, and infrared detectors [4–6]. Dithiocarbamate ligands exhibiting diverse structural functions (monodentate, bidentate-terminal, bidentate-bridging, and tridentate-bridging) and mercury(II) cations (electronic configuration d10) form
complexes characterized by com
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