Structures and properties of functional metal selenites and tellurites

Metal selenites and tellurites are a class of very important compounds. In this paper, the structures and properties of metal selenites or tellurites combining with transition-metal (TM) ions with the d (0) electronic configuration or tetrahedral MO 4 building blocks of post-transition main-group elements were reviewed. Most compounds in the alkali or alkaline-earth-d (0) TM-Se (IV) (or Te (IV))-O systems exhibit extended anionic architectures composed of distorted octahedra of (d (0)) TM cations and tellurite or selenite groups. The distortion of the octahedron is always away from the lone-pair cation, and some of them exhibit excellent second-order nonlinear optical properties due to the adductive effects of two types of bond polarizations. Because of the high coordination number of Ln (III) ions, most of compounds in the Ln-d (0) TM-Se (IV) (or Te (IV))-O systems are not second-harmonic-generation active; however, they are able to emit strong luminescence in the visible or near-IR region; also in most cases, the d (0) TM cations are in tetrahedral geometry and are well separated from selenite or tellurite groups. It is also interesting to note that the selenite group is normally "isolated", whereas the TeO x ( x = 3-5) can be polymerized into a variety of discrete polynuclear anionic clusters or extended architectures via Te-O-Te bridges.     

Syntheses and crystal structures of a series of alkaline earth vanadium selenites and tellurites

Six new novel alkaline-earth metal vanadium(V) or vanadium(IV) selenites and tellurites, namely, Sr(2)(VO)(3)(SeO(3))(5), Sr(V(2)O(5))(TeO(3)), Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O), Ba(3)(VO(2))(2)(SeO(3))(4), Ba(2)(VO(3))Te(4)O(9)(OH), and Ba(2)V(2)O(5)(Te(2)O(6)), have been prepared and structurally characterized by single crystal X-ray diffraction analyses. These compounds exhibit six different anionic structures ranging from zero-dimensional (0D) cluster to three-dimensional (3D) network. Sr(2)(VO)(3)(SeO(3))(5) features a 3D anionic framework composed of VO(6) octahedra that are bridged by SeO(3) polyhedra. The oxidation state of the vanadium cation is +4 because of the partial reduction of V(2)O(5) by SeO(2) at high temperature. Ba(3)(VO(2))(2)(SeO(3))(4) features a 0D [(VO(2))(SeO(3))(2)](3-) anion. Sr(V(2)O(5))(TeO(3)) displays a unique 1D vanadium(V) tellurite chain composed of V(2)O(8) and V(2)O(7) units connected by tellurite groups, forming 4- and 10-MRs, whereas Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O) exhibits a 2D layer consisting of [V(4)O(14)] tetramers interconnected by bridging TeO(3)(2-) anions with the Sr(2+) and water molecules located at the interlayer space. Ba(2)(VO(3))Te(4)O(9)(OH) exhibits a one-dimensional (1D) vanadium tellurite chain composed of a novel 1D [Te(4)O(9)(OH)](3-) chain further decorated by VO(4) tetrahedra. Ba(2)V(2)O(5)(Te(2)O(6)) also features a 1D vanadium(V) tellurites chain in which neighboring VO(4) tetrahedra are bridged by [Te(2)O(6)](4-) dimers. The existence of V(4+) ions in Sr(2)(VO)(3)(SeO(3))(5) is also confirmed by magnetic measurements. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory (DFT) methods indicate that all six compounds are wide-band gap semiconductors.     

Tracer-diffusion of Mn2+ ions in agar gel containing alkali metal chlorides

Prompt gamma-neutron activation analysis, PGNAA, has been used to determine major and minor elements of bituminous coals. Calibration curves for H, C, N, Cl, Si, Ti, Al, Fe, Ca, Na, K, and S were obtained using six coals of different origin. The correlation coefficients are, in general, greater than 0.9 with the exception of C, N, and K. The -peak intensities were corrected for volume hydrogen content and normalised to the source intensity by using the 2615 keV -line from the (n, n) reaction induced in the lead container of the Cf source. Elemental compositions of new coal samples were determined. In spite of the weak neutron source intensity, the comparison between the elemental concentrations measured by PGNAA and by conventional analysis show good agreement except for N, K, S and Ca.     

Complexes of liquid crystal o-hydroxyazo compounds with Cu2+ and Pd2+ ions

Liquid crystal o-hydroxyazo compounds were prepared and used to give complexes with Cu²⁺ and Pd²⁺ ions. The structures of these complexes were studied by ESR, IR, and UV spectroscopy. The relationship of the structures of these complexes and their mesogenic properties was examined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2871–2874 December, 1991.     

Technetium removal from the aqueous solution using zeolites A and Y containing transition metal ions Co2+ and Zn2+

Journal of Radioanalytical and Nuclear Chemistry - The adsorption properties of two zeolite types, faujasite (NaY, ZnY, CoY) and LTA-4A zeolite (NaA, ZnA, CoA), towards technetium were studied in...     

Chiral distinction in square planar Pt and Pd complexes of 2,2′-bipyridine derivatives

A computational study of square planar organometallic complexes formed by the ligand 2,2′-bipyridine and all its possible difluoro derivatives in analogous position of the aromatic rings (n,n′-difluoro-2,2′-bipyridine, where n = n′ = 3, 4, 5, and 6) and two M–X₂ (M = Pd and Pt and X = F, Cl, Br, and I) fragments has been carried out amounting to a total of 80 complexes. Relationships have been found between the chiral distinction energy and the different chemical moieties present. Using the statistical Free-Wilson method, the relative energies between the diastereomeric complexes have been correlated with the position of the substituent, the counter anion, and the central metal cation.     

EPR parameters and local geometry for Cr3+ and V2+ ions in HfS2 crystals

From the high-order perturbation formulas of EPR parameters (zero-field splitting D, g factors gparallel, gperpendicular and hyperfine structure constants Aparallel, Aperpendicular) based on the two spin-orbit coupling parameter model for 3d3 ions in trigonal symmetry, the EPR parameters of Cr3+ and V2+ ions in HfS2 crystals are calculated. From the calculations, it is found that the local trigonal distortion angle theta of impurity center in HfS2:Cr3+ is smaller than that in HfS2:V2+. The dominant cause of the small zero-field splitting |D| and g-anisotropy |Deltag|=|gparallel-gperpendicular| in HfS2:Cr3+ (compound to HfS2:V2+) is due to the small local trigonal distortion angle theta rather than to the small impurity-ligand distance R in HfS2:Cr3+.     

Oligomeric acetylacetonate complexes containing Tb3+ and Co2+ or Ni2+ ions

Molecular weight measurements and the visible absorption spectra of mixed solutions of Tb(aa)₃ 3H₂O and Co(aa)₂ in benzene indicate that these complexes interact to form mixed metal oligomeric species. The slow decrease in Tb³⁺ ion phosphorescence after mixing the individual solutions supports this interpretation. Similar investigations with Ni(aa)₂ also provide evidence for mixed metal oligomeric complexes. Crystalline compounds with analyses corresponding to the stoichiometries CoTb(aa)₅3H₂O and NiTb(aa)₅3H₂O have been isolated from benzene solution.     

Evidence for d orbital aromaticity in square planar coinage metal clusters

Quantitative evidence for the existence of aromaticity involving the d orbitals of transition metals is provided for the first time. The doubly bridged square planar (D(4)(h)()) coinage metal clusters (M(4)Li(2), M = Cu (1), Ag (2), and Au (3)) are characterized as aromatic by their substantial nucleus independent chemical shifts (NICS) values in the centers (-14.5, -14.1, and -18.6, respectively). Nevertheless, the participation of p orbitals in the bonding (and cyclic electron delocalization) of 1-3 is negligible. Instead, these clusters benefit strongly from the delocalization of d and to some extent s orbitals. The same conclusion applies to Tsipis and Tsipis' H-bridged D(4)(h)() Cu(4)H(4) ring (4). Canonical MO-NICS analysis of structures 1-3 shows the total diatropic d orbital contributions to the total NICS to be substantial, although the individual contributions of the five sets of filled d orbitals vary. The d orbital aromaticity of Cu(4)Li(2) also is indicated by its atomization energy, 243.2 kcal/mol, which is larger than Boldyrev's doubly (sigma and pi) aromatic Al(4)Li(2) (215.9 kcal/mol).     

Epoxy-based oligomer containing dithia-aza-based naphthylazobenzene pendant: a chemosensor for Hg2+ and Cu2+ ions

A simple epoxy-based oligomer 1 containing naphthylazobenzene-appended dithia-aza moieties was prepared. In UV–vis measurements, the proposed oligomer showed the ion-sensing ability to Hg²⁺ and Cu²⁺ ions. The discrimination between two differently responding Hg²⁺ and Cu²⁺ ions was also realised from ‘ON–OFF’ type fluorescence responses of 1.     

New fluorescent probes for the detection of mixed sodium and potassium metal ions

A new fluorescent probe 2 is developed that is capable of measuring the concentration of a mixture of sodium and potassium ions in the solution. This probe contains a fluorophore that is utilized in two ways depending on the pH of the solution.     

Conductance in isodielectric mixed solvents containing triple ions

Formation of higher ion aggregates mainly by hydrogen bonding in solutions of diethylcyclohexylammonium chloride (c-Hex(Et)₂NHCl) has been examined by conductometry in nearly isodielectric mixed solvents: nitrobenzene-acetonitrile (35) and benzonitrile-ethanol (25) at 25°C. At lower acetonitrile content (less than ca. 10% by volume) in mixtures with nitrobenzene the salt gave minimum in the molar conductivities over the concentration range 4x10^–3 to 0.12 mol-dm^–3 which were explained by ion pair (MX), triple ion (M₂X, MX₂), and quadrupole (M₂X₂) formation in the solvent mixtures. The formation constants of the ion aggregates decreased with increasing content of acetonitrile. In benzonitrile-ethanol mixtures, the degrees of ion aggregate formation also decreased with increasing content of ethanol; triple ion formation could not be observed at more than 20% ethanol.     

Synthesis and characterization of a novel tantalum chalcogen-rich molecular cluster with square planar metal core

Black single crystals of Ta(4)Se(9)I(8) are obtained in a high yield by heating Ta, Se, and I(2) at 300 degrees C in 1:2.2:1.0 molar ratio. In the structure, the tantalum atoms form a square, with four Se(2) ligands bridging the Ta-Ta edges and one capping the square. Each Ta atom has two terminal iodine atoms. The compound is diamagnetic and has only two electrons for metal-metal bonding.     

Tracer-diffusion of Zn2+ ions in some transition metal sulphates

Tracer-diffusion of Zn²⁺ ions is studied in zinc, manganese and copper sulphates over a concentration range of 10^–4 to 0.25M using 1% agar gel medium at 25 °C. A comparison of the experimental and theoretical values of tracer-diffusion coefficients shows a deviation from the theory. This is explained in the light of different types of interactions occurring in the ion-gel-water system. The effect of supporting electrolytes and its concentration on the obstruction effect in the tracer-diffusion of zinc ions is also examined. The obstruction effect decreases with increasing charge density of the cation of the electrolytes at a given concentration and for a particular elecrolyte it decreases with its concentration. These observations are accounted on the basis of competitive hydration between ions and agar macromolecules.     

Tetradecker transition metal complexes containing double planar hexacoordinate carbons and double planar heptacoordinate borons

A theoretical investigation on tetradecker transition metal complexes of Cp-Fe-CB6-Fe-CB6-Fe-Cp (1) containing double planar hexacoordinate carbons and Cp-Fe-BB7-Fe-BB7-Fe-Cp (2) containing double planar heptcoordinate borons has been performed in this work at density functional theory level. [CpFe]+ monocations prove to effectively stabilize these unusual complexes, which are mainly maintained by effective d-pi coordination interactions between the partially filled Fe 3d orbitals and the delocalized pi molecular orbitals (MOs) of the four planar deckerlike ligands. The results obtained in these model computations expand the domain of ferrocene chemistry and could provide a new approach for synthesizing planar hyper-coordinate carbons and borons in transition metal complexes.     

Paper chromatography of metal ions in solvents containing methylamine

Summary The effect of methylamine and methylamine hydrochloride has been systematically investigated in the paper chromatography of various metal ions. It has been found that methylamine hydrochloride like EDTA helps in preventing tailing. A new separation of Fe, Mn, Ni, and Co has been developed. The R_f-values are 0.97, 0.49, 0.08, 0.79 respectively and the solvent system used is ethylacetoacetate/methylamine hydrochloride/conc. hydrochloric acid (2027). The values are equally spaced, the spots are compact and the separation is probably the best yet recorded.

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Zusammenfassung Es wird über eine systematische Untersuchung des Einflusses von Methylamin und Methylaminhydrochlorid bei der Papierchromatographie verschiedener Metallionen berichtet. Dabei ergab sich, da\ Methylaminhydrochlorid Ähnlich wie ÄDTA zur Verhinderung der Schwanzbildung benutzt werden kann. Zur Trennung von Fe, Mn, Ni und Co wird ein Lösungsmittel aus Acetessigester, Methylaminhydrochlorid und konz. SalzsÄure (2027) empfohlen (R_f-Werte: 0,97, 0,49, 0,08 bzw. 0,79), mit dem sehr gute Ergebnisse erzielt wurden.

     

A tetranuclear heterobimetallic square formed from the cooperative ligand binding properties of square planar and tetrahedral metal centers

Reaction of Rh(I) and Zn(II) metal centers with a ligand containing salicylaldiminato and thioether-phosphine moieties resulted in the formation of a tetranuclear heterobimetallic molecular square. The directionality required to form these structures is imparted by both the tetrahedral and square planar metal centers acting in concert with one another.     

Tracer-diffusion of Co2+ ions in some transition metal chloride solutions

Tracer-diffusion coefficients of Co²⁺ ions have been determined in 1% agar gel containing transition metal chlorides, viz. ZnCl₂, NiCl₂ and MnCl₂ over the concentration range of 10^–6–0.15 M at 25°C using the zone-diffusion technique. The results are compared with calculated values on the basis of Onsager's theory and the deviations are accounted for on the basis of various types of interactions in the ion-gel water system. Further, activation energy for the tracer-diffusion of Co²⁺ ions in the above mentioned electrolytes has been obtained as a function of electrolyte concentration, using measurements in the temperature range of 25–50°C. The trend in activation energy is explained on the basis of the WANG's model.