卷 49, 编号 2 (2023)

The possibility of preparing thin films of cobalt(II) cage complex (clathrochelate) that undergoes a temperature-induced spin transition by thermal sublimation was demonstrated using UV spectroscopy. The films were more uniform and more thermally stable than the films formed by centrifugation of the solution on a substrate surface. In combination with scanning electron microscopy data, this revealed the dependence of the spin transition temperature on the method of film preparation and dependence of the supramolecular organization in the films on the substrate material, indicating that transition metal clathrochelates show the spinterface effect at the interface with a metal electrode. In addition to the possibility of controlling the magnetic properties of this unique class of coordination compounds by molecular design methods, this effect opens up broad opportunities for creating molecular spintronic devices with characteristics tailored for the researcher requirements.

The double Au(III)–Ag(I) complex crystallizing as the solvated form of [Au{S2CN(CH2)5}2]2[Ag2Cl4]· CH2Cl2 (I) was obtained by the reaction of silver(I) N,N-pentamethylenedithiocarbamate with a solution of Na[AuCl4]/5.15 M NaCl. According to X-ray diffraction data (CIF file CCDC no. 2062810), the structural units of the compound are nonequivalent [Au{S2CN(CH2)5}2]+ cations (noncentrosymmetric A and centrosymmetric B and C in a ratio of 2 : 1 : 1), cyclic tetrachlorodiargentate(I) anions, [Ag2Cl4]2–, and solvating CH2Cl2 molecule. The latter is retained in the structure due to two nonequivalent C–H···Cl hydrogen bonds formed with the cyclic [Ag2Cl4]2– anion involving its terminal Cl(1) and bridging Cl(2) chlorine atoms. The supramolecular self-organization of I is based on a system of multiple Ag···S and Cl···S secondary interactions that сombine the ionic structural units of the complex into an intricate two-dimensional pseudopolymer layer. A study of the thermal behavior of I by simultaneous thermal analysis established the conditions for quantitative reduction of bound gold(III) and silver(I). The studied Au(III)–Ag(I) compound exhibits a high level of biological activity against the nonpathogenic M. smegmatis strain.

A procedure for the synthesis of the new ditopic ligand combining in the structure 1- and 5-substituted tetrazolyl cycles, 5-(2-(1H-tetrazol-1-yl)phenyl)-1H-tetrazole (HL), is developed. The coordination compounds of Co(II) and Cu(II) halides [Co(HL)2Cl2], [Cu(HL)2Cl2], [Cu(HL)2Br2], and [CuL2(H2O)]n based on ligand HL are synthesized. The complexes are studied by elemental analysis, diffuse reflectance spectroscopy, IR spectroscopy, X-ray diffraction (XRD), and static magnetic susceptibility. The crystal structure of the molecular coordination polymer [CuL2(H2O)]n is determined by XRD (CIF file CCDC no. 2127210). The temperature and field dependences of the magnetization show that the magnetic properties of the synthesized Cu(II) complexes are due to exchange interactions in one-dimensional chains of the copper ions (S = 1/2). For complex [Cu(HL)2Br2], the parameters are shifted toward the enhancement of the antiferromagnetic interaction compared to the analog containing the chloride ion.