6 resultados para TELLURIDE

em Deakin Research Online - Australia


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Yellow crystals of the title compound, C20H14Te, were obtained serendipitously in an attempt to recrystallize the reduction product of (1-C10H7)[(CH(Me)COC6H5)]TeCl2 from dichloromethane. The molecule exhibits an angular geometry with almost equal Te-Caryl bonds and a C-Te-C angle close to values observed for other diaryl tellurides. One of the aromatic ring systems lies in the C-Te-C plane and the other is oriented at 76.81 (6)°, giving an almost T-shaped conformation that is compatible with the steric demand of 1-naphthyl ligands.

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A new ternary compound with composition Cu5Sn2Te7 has been synthesized using the stoichiometric reaction of Cu, Sn, and Te. The compound crystallizes in C2 space group with unit cell parameters of a = 13.549(2) Å, b = 6.0521(11) Å, c = 9.568(2) Å, and β = 98.121(2)°. Cu5Sn2Te7 is a superstructure of sphalerite and exhibits tetrahedral coordination of Cu, Sn, and Te atoms, containing a unique adamantane-like arrangement. The compound is formally mixed valent with a high electrical conductivity of 9.8 × 10(5) S m(-1) at 300 K and exhibits metallic behavior having p-type charge carriers as indicated from the positive Seebeck coefficient. Hall effect measurements further confirm holes as charge carriers with a carrier density of 1.39 × 10(21) cm(-3) and Hall mobility of 4.5 cm(2) V(-1) s(-1) at 300 K. The electronic band structure calculations indicate the presence of a finite density of states around the Fermi level and agree well with the p-type metallic conductivity. Band structure analysis suggests that the effective mass of the hole state is small and could be responsible for high electronic conductivity and Hall mobility. The high thermal conductivity of 15.1 W m(-1) K(-1) at 300 K coupled with the low Seebeck coefficient results in a poor thermoelectric figure of merit (ZT) for this compound. Theoretical calculations indicate that if Cu5Sn2Te7 is turned into a valence precise compound by substituting one Cu by a Zn, a semiconducting material, Cu4ZnSn2Te7, with a direct band gap of ∼ 0.5 eV can be obtained.

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Pinacolyltellurium(IV) dihalides, (t-BuCOCH2)2TeX2 (X ) Br (1b), I (1c)) and Ar(t-BuCOCH2)TeCl2 (Ar == 1-C10H7 (Np) (2a), 2,4,6-Me3C6H2 (Mes) (3a)), are readily prepared at room temperature by the oxidative insertion of elemental tellurium into the Csp3-Br or -I bond of the α-halopinacolone and by the reaction of ArTeCl3 with the pinacolone t-BuCOCH3. The bromides Np(t-BuCOCH2)TeBr2 (2b) and Mes(t-BuCOCH2)TeBr2 (3b) can be prepared by the addition of bromine to the telluride Ar(t-BuCOCH2)-Te or of α-bromopinacolone to ArTeBr. Variable-temperature 1H and 13C NMR of the separate signals for the o-Me groups in 3a,b indicate a very high barrier to rotation about the Te-C(aryl) bond. Crystal diffraction data for 1c, 2a-c, and 3b show that intramolecular 1,4-Te …O(C) secondary bonding interactions (SBIs) are retained even in the presence of bulky aryl groups and intermolecular Te …X SBIs are subject to electronic population and steric congestion around the Te(IV) center in the solid state.

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Monomeric tellurides 4-RC6H4(SB)Te [SB = 2-(4,4'-N02C6H4CH=NC6H3-Me); R = H, 1a; Me,1b; OMe, 1c], which incidentally represent the first example of a telluride with 1,4-Te···N intramolecular interaction, have been prepared and characterized by solution and solid-state 125Te NMR, 13C NMR and X-ray crystallography. Interplay of weak C-H···O and C-H-··π{ interactions in the crystal lattice of 1b and1c are responsible for the formation of supramolecular motifs. These tellurides undergo expected oxidative addition reactions with halogens and interhalogens and also interact coordinatively with mercury(II) halides to give 1:2 complexes, HgX2[4-RC6H4(SB)Te]2 (X = CI, R = H, 2a; Me, 2b; OMe, 2c and X = Br, R = H, 3a; Me, 3b; and OMe, 3c) with no sign of Te-C bond cleavage, as has been reported for some 1,5-Te·· ·N(O) intramolecularly bonded tellurides. The complexes 2a and 3c are the first structurally characterized monomeric 1:2 adducts of mercury(II) halides with Te ligands. The 1,4-Te···N intramolecular interactions in the solid-state are retained in the complexes highlighting simultaneously the Lewis acid and base character of the Te(lI) atom. Packing of molecules in the crystal lattice of 2a
and 3c reveals that non-covalent C-H· . ·Cl/Br interactions involving metal-bound halogen atoms possess significant directionality and in
combination with coordinative covalent interactions may be of potential use in creating inorganic supramolecular synthons.

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Electrophilic substitution of acylmethanes (methyl ketones), RCOCH3 (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl3 (Ar = 1-C10H7, Np, A; 2,4,6-Me3C6H2, Mes, B; 4-MeOC6H4, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH2)ArTeCl2. Reduction of the dichlorides, gives tellurides, (i-PrCOCH2)ArTe, 1A–1C, which give the corresponding dihalides, (i-PrCOCH2)ArTeX2 (X = Cl, 1Aa–1Ca; Br, 1Ab–1Cb; I, 1Ac–1Cc) when reacted in situ with SO2Cl2, Br2 or I2. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar2Te2 except in the case of (i-PrCOCH2)MesTe ( 1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate 1H and 13C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te–C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one 125Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1Ca and 1Cc which are indicative of the presence of intramolecular TeO secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te–C(mesityl) bond axis. Intermolecular C–HO H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.

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Bi2Te3 based alloy nanosheet (NS)/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) composite films were prepared separately by spin coating and drop casting techniques. The drop cast composite film containing 4.10 wt % Bi2Te3 based alloy NSs showed electrical conductivity as high as 1295.21 S/cm, which is higher than that (753.8 S/cm) of a dimethyl sulfoxide doped PEDOT:PSS film prepared under the same condition and that (850-1250 S/cm) of the Bi2Te3 based alloy bulk material. The composite film also showed a very high power factor value, ∼32.26 μWm(-1) K(-2). With the content of Bi2Te3 based alloy NSs increasing from 0 to 4.10 wt %, the electrical conductivity and Seebeck coefficient of the composite films increase simultaneously.