卷 43, 编号 10 (2017)

The X-ray diffraction and magnetochemical studies of the acetate-bridged binuclear copper(II) complex with 1,3-bis(3-formyl-5-tert-butylsalicylidenimino)propanol-2 with a nearly planar structure of the exchange fragment are carried out (СIF file CCDC 940849). The assumption that the magnetic exchange in the complexes with the anticomplementary carboxylate exogenic bridges 1,3-O,O' is determined only by the structural factors and the bridging coordination of the solvent molecule changes the type of the exchange interaction between the copper(II) ions is proved to be true.

Crystalline polymeric thallium(I) morpholinedithiocarbamate [Tl₂{S₂CN(CH₂)₄O}₂]_n (I) and the heteronuclear ion–polymeric gold(III)–thalium(III) complex ([Au{S₂CN(CH₂)₄O}₂][TlCl₄])_n (II) are preparatively isolated and characterized by X-ray diffraction analysis and ¹³C MAS NMR spectroscopy. According to the X-ray diffraction data, the main structural units of compounds I and II (CIF files CCDC 1548079 and 1548080) are presented by the binuclear centrosymmetric molecule [Tl₂{S₂CN(CH₂)₄O}₂], noncentrosymmetric complex cation [Au{S₂CN(CH₂)₄O{₂]⁺, and isomeric complex anions [TlCl₄]^–. The formation of the three-dimensional polymeric structure (coordination number of Tl is 7), which is not characteristic of thallium(I) dithiocarbamates, is a consequence of the participation of the secondary Tl…O and Tl…S bonds of two types in the supramolecular self-organization of compound I. Nonequivalent secondary interactions of the first type join the binuclear molecules [Tl₂{S₂CN(CH₂)₄O}₂] into polymer layers, which, in turn, form the three-dimensional polymeric framework due to the secondary bonds Tl…S. The revealed ability of freshly precipitated compound I to the chemisorption of gold(III) from solutions (2 M HCl) makes it possible to obtain heteronuclear supramolecular complex II as an individual form of binding. In the structure of the latter, the pairs of stronger secondary Au…S bonds join the gold(III) cations into dimers [Au₂{S₂CN(CH₂)₄O}₄]²⁺ of the angular structure, the structural ordering of which is achieved in the cationcationic polymeric chain ([Au₂{S₂CN(CH₂)₄O}₄]²⁺)_n of the helical type involving the pairs of less strong Au…S bonds between the adjacent binuclear units. The distorted tetrahedral anions [TlCl₄]^– are localized between the polymeric chains. The study of the thermal behavior of compounds I and II by simultaneous thermal analysis makes it possible to establish the character of thermal transformations of the substances and to identify Tl₂S (I), TlCl, and elemental gold (II) as thermolysis products.

The influence of the aggregate state on the IR luminescence is studied for the Nd(III), Sm(III), and Yb(III) complexes with the thienyl, phenyl, and alkyl derivatives of acetylacetone in solutions and as sorbates on the polymer matrix. It is found that the luminescence intensity of the sorbates of the complexes is 2–3 orders of magnitude higher than that in solutions due to the elimination of diffusion and respective intermolecular nonradiative losses of the excitation energy.

Three coordination complexes [Co(Imphtpy)₂]Cl₂ · CHCl₃ · 3H₂O (I), [Ni(Imphtpy)₂]Cl₂ · CHCl₃ · C₂H₅OH (II) and [Zn(Imphtpy)]Cl₂ (III) (Imphtpy = 4'-(4-(imidazol-1-yl)phenyl)2,2':6',2″-terpyridine) have been synthesized and characterized by IR, elemental analysis and X-ray single crystal diffraction (СIF files CCDC nos. 1012055 (I), 1011708 (II), 1011709 (III)). Complexes I and II are isomorphism except for some solvent molecules. In the crystal, both face-to-face interactions between pyridyl ring, imidazole rings and phenyl rings and hydrogen bonds facilitate the construction of 3D networks. There are no hydrogen bonds in III and the packing of discrete neutral molecules were ascribed to face-to-face interactions and van der Waals forces. The luminescence properties of three complexes have been investigated in the solid state at room temperature.

Two polymeric frameworks, [Zn(Dpb)(Oba)]_n (Ι) and [Cd(Dpb)(2,6-Pda)H₂O]_n · nH₂O (II) (Dpb = 1,4-bis(pyridin-3-ylmethoxy)benzene, H₂Oba = 4,4'-oxybis(benzoic acid), 2,6-H₂Pda = 2,6-pyridyl-dicarboxylate), have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction method (CIF files CCDC 1488269 (Ι), 1488270 (II)). Complex Ι is a 2D layer structure, which is constructed from 1D double chain. Complex II is a 1D chain. The luminescent properties of Ι, II have been investigated with fluorescent spectra in the solid state, I and II displayed a strong fluorescent emission at room temperature.

A new macrocyclic oxamido carboxylate metalloligand was designed and three heteronuclear coordination polymers of the metalloligand and metal nodes Cu²⁺, Zn²⁺ and Cd²⁺ were prepared. X-ray single crystal analyses (CIF files CCDC nos. 1025722–1025724 for I–III) revealed that multiple favourable features endowed the metalloligand with a strong power to force the metal nodes to generate 1D helical coordination polymers. Thermogravimetric analyses showed that the complexes with Cu²⁺ and Zn²⁺ nodes exhibited moderate thermal stability. The three complexes were also characterized by IR spectra and PXRD.