Том 45, № 10 (2019)

Experimental and experimental–theoretical studies (using the molecular invariom) of the electron density distribution are performed for the η⁶-[3-acetyltetrahydro-6-phenyl-2Н-1,3-oxazine]tricarbonylchromium(0) complex. The topological characteristics of the electron density (ρ(r), ∇²ρ(r)) at the critical points (3, –1) coincide in the experimental and experimental–theoretical distributions within the “transferability indices.” The experimental–theoretical study more reliably localizes the “expected” critical points (3, –1) between the chromium atom and arene ligand.

The crystalline heteroleptic bismuth(III) complexes, [Bi{S₂CN(iso-C₄H₉)₂}₂(NO₃)] (I) and [Bi{S₂CN(C₃H₇)₂}₂Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and (¹³C, ¹⁵N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ₂-bridging function participate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III) binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are characterized by the eightfold [BiS₄O₄] (I) or sixfold [BiS₄Cl₂] (II) environment. The thermal behavior of the synthesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of thermogravimetry and differential scanning calorimetry curves. In both cases, Bi₂S₃ is the only final product of the thermal transformations of compounds I and II.

The synthesis of complexes LnI(C₆F₅O)₂ and LnCp(L)₂ (Ln = Er, Yb; L = C₆F₅O, SON^F), which are convenient precursors for the preparation of heteroligand bimetallic complexes, is described. The structures of YbI(C₆F₅O)₂(DME)₂ (I), CpEr(C₆F₅O)₂(DME)[(C₂H₅)₂O] (III), and CpYb(SON^F)₂(DME) (VI) were established by X-ray diffraction (CIF files CCDC (nos. 1902963 (I), 1902964 (III), and 1902965 (VI)). The developed methods were used to prepare heteroligand bimetallic Yb(III)–Er(III) complexes (C₆F₅O)₂Yb[µ-(CF₃)₂CHO]₂Er(C₆F₅O)₂ and {(SON^F)₂Yb[µ-(CF₃)₂CHO]₂-Er(SON^F)₂}_x, which showed metal-centered emission inherent in Yb³⁺ and Er³⁺ ions λ_em = 985 and 1540 nm, respectively. This suggests that the obtained compounds can serve as promising upconversion materials.

The reaction of the amidinatehydride complex of divalent ytterbium [(Amd)Yb^II(μ²-H)]₂ (Amd is {tert-BuC(NC₆H₃-iso-Pr₂-2,6)₂}) with BPh₃ proceeds with the cleavage of the B−C bonds and affords the Yb(II)[(Amd)Yb^II(μ²-H₃BPh)]₂ complex containing the phenyltrihydroborate anion [PhBH₃]⁻. The X-ray diffraction analysis (СIF file CCDC no. 1902290) shows that the [PhBH₃]⁻ anions in the complex are bridging. The “nonclassical” κ¹-amido-η⁶-arene coordination mode to the Yb²⁺ ion is retained for the amidinate ligand.

Two transition-metal coordination polymers {[Zn₂(L)₂(HCOO)₂]}_n (I) and {[Cd₂(L)₃(HCOO)] ∙ 2H₂O}_n(II) (L = 1,3-bis(4-(methoxycarbonyl)benzyl)-1H-imidazol-3-ium anion) have been synthesized via solvo-thermal method. Both of the coordination polymers I and II were characterized by single-crystal X-ray diffraction (CIF files CCDC nos. 1834629 (I) and 1834630 (II)), FT-IR spectroscopy, elemental analysis and thermogravimetric analysis. The results shown compound I is a two dimensional sql layer structure containing interlocking structure between the left and right helix chains, and compound II is rare three dimensional six-fold interpenetrating dia topology framework. Luminescence investigations revealed that both of compound I and II emitted blue light.