Sergey A. Adonin

Binuclear Bi(III) halide complexes with 4,4′-ethylenepyridinium cations: luminescence tuning by reversible solvation

Two new complexes based on 4,4′-ethylenepyridinium cations and binuclear Bi(III) anionic complexes, (H2bpe)2[Bi2X10]·2H2O (bpe = 1,2-bis(4-pyridyl)ethane; X = Cl (1), Br (2)), have been synthesized and characterized by X-ray diffractometry. In both cases, loss of solvent H2O molecules affects the luminescence behavior, resulting in increase of intensity (ca. 5-fold). Desolvation is reversible, which is of potential use in chemosensor systems.

New {RuNO} Polyoxometalate [PW11O39RuII(NO)]4-: Synthesis and Reactivity

New Ru-containing polyoxometalate [PW11O39Ru(II)(NO)](4-) (1(4-)) was obtained in high yield by reaction of [Ru(NO)Cl5](2-) with [PW11O39](7-) and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in 1(4-) toward various reagents has been studied using a versatile and simple ESI tandem mass spectrometric methodology for identification of the L attached at the Ru site; this approach relies on the preferential liberation of the L ligands attached at the Ru sites upon mass-selecting desired intermediates and subsequent promotion of their fragmentation. Reactions with both hydrazine and hydroxylamine lead to elimination of the nitroso group and quantitative formation of [PW11O39Ru(III)(H2O)](4-) (2(4-)) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH3-coordinated [PW11O39RuNH3](4-) (3(4-)) complex was achieved upon reduction of 1(4-) with Sn(2+) in water.

New polyoxotantalate salt Na 8 [Ta 6 O 19 ]·24.5H 2 O and its properties

The interaction of Ta2O5 with sodium hydroxide at 400°C yields Na8[Ta6O19], which can be recrystallized from an aqueous solution in the form of Na8[Ta6O19]·24.5H2O. The complex is characterized by IR spectroscopy, thermogravimetry, powder XRD, and single crystal XRD: hexagonal system, P63 space group, a = 12.3622(2) Å, c = 31.4305(7) Å, V = 4159.81(13) Å3, dx = 3.217 g/cm3, R = 0.0195.

Trinuclear Iodobismuthate Complex (Na 3 (Me 2 CO) 12 )(Bi 3 I 12 ): Synthesis and Crystal Structure

The reaction of BiI3 and NaI in acetone gives a trinuclear iodobismuthate complex, [Na3(Me2CO)12][Bi3I12] (I), which was studied by X-ray diffraction (CIF file CCDC no. 996330). The centrosymmetric [Bi3III I12]3− anions are groups of three distorted {BiI6} octahedra coupled at the faces. The sodium cations combine six Me2CO molecules in the bidentate bridging mode to give linear trimers in which the side sodium ions coordinate six terminal acetone molecules.

Halogen Contacts‐Induced Unusual Coloring in BiIII Bromide Complex: Anion‐to‐Cation Charge Transfer via Br⋅⋅⋅Br Interactions

A yellow bromobismuthate {(2-BrPy)2 H}[BiBr4 ] (1, 2-BrPy=2-bromopyridinium) transforms into the unusually deeply colored cherry-red (2-BrPyH)2 [BiBr5 ] (2). A combination of structural studies and theoretical calculations confirms that the appearance of short non-covalent Br⋅⋅⋅Br interactions (≈3.3 Å) in 2 is responsible for the anion-to-cation charge transfer (LP(Brligand )→σ*(Br-C)), yielding dramatic changes in optical behavior. This effect opens the way towards novel halogen bonding-templated halometalate-based hybrid materials with enhanced optical properties.

Heterogeneous bromination of alkenes using Bi(III) polybromide complexes as {Br2} source

A new polybromide Bi(III) complex (PyH)3{[Bi2Br9](Br2)} was synthesized and characterized by XRD and other methods. This compound is able to act as a selective bromination agent towards various types of substituted alkenes.

Polymer chlorobismuthate complex catena-{((Me,Me)Bpe)[BiCl5]}n: Synthesis and crystal structure

The reaction of BiCl3 and N,N-dimethyl-1,2-bis(pyridyl)ethane chloride (Me,Me-Bpe) in 2 M HCl affords a polymer chlorobismuthate complex {((Me,Me)Bpe)[BiCl5]}n (I). The structure of complex I is determined by X-ray diffraction analysis (CIF file CCDC 1058842). The anionic moiety of the complex is presented by a 1D coordination polymer ([BiCl5]2n–)n consisting of octahedral blocks {Cl6} linked by µ2- bridging chloride ligands into infinite zigzag chains.

Iodobismuthate complex (Bu4N)3[Bi3I12]: Crystal structure of a new polymorph

The structure of a new polymorph of the trinuclear iodobismuthate complex TBA3[Bi3I12] (TBA = tetra-n-butylammonium) (1) synthesized by the reaction of BiI3+TBA-I in the presence of silver triflate is identified.

One-dimensional polymeric polybromotellurates(IV): structural and theoretical insights into halogen⋯halogen contacts

Reactions of TeO2 and Br2 in concentrated HBr in the presence of various organic cations resulted in the formation of one-dimensional supramolecular polymers with the structure cation2{[TeBr6](Br2)}. In the crystal structures, the Br2 units are connected to [TeBr6]2− octahedra via halogen–halogen contacts, building linear chains of two different geometries. The nature of the Br⋯Br, Br⋯Cl, and Cl⋯Cl contacts in the present and previously reported complexes of this family was investigated by theoretical methods, allowing the estimation of their energies (0.9–3.8 kcal mol−1).

Polyoxomolybdate-supported bismuth trihalides [Mo8O26(BiX3)2](4-) (X = Cl, Br, I): syntheses and study of polymorphism.

Octamolybdate complexes TBA4[Mo8O26(BiX3)2] (TBA = n-tetrabutylammonium, X = Cl (1), Br (2), I (3)) were obtained by straightforward syntheses from TBA4[Mo8O26] and corresponding Bi(III) halides in MeCN. All compounds were structurally characterized; in all cases, {BiX3} fragments are coordinated by two oxygen atoms of polyoxometalate core. Occurring polymorphism is also discussed.