RESUMO
A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.
RESUMO
A method for obtaining perchlorinated di-S,S-substituted derivatives of the closo-decaborate anion with various alkyl groups has been developed: [B10Cl9SR2]- (R= i-C3H7, n-C3H7, n-C4H9, n-C8H17, n-C12H25, n-C18H37, CH2Ph, and cyclo-S(CH2)4). The method is based on the preparation of the sulfonium-substituted anion [B10H9SR2]- by alkylation of the anion [B10H9SH]2- with bromoalkanes (i-C3H7Br, n-C3H7Br, n-C4H9Br, n-C8H17Br, n-C12H25Br, n-C18H37Br, PhCH2Br, and BrCH2(CH2)2CH2Br) followed by the cluster chlorination with sulfuryl chloride SO2Cl2 in acetonitrile. The process proceeds until the hydrogen atoms in the boron cluster are completely replaced with chlorine and completes within 60 h. It has been found that the melting point of salts ((C4H9)4N)[B10Cl9SR2] (R= i-C3H7, n-C3H7, n-C4H9, n-C8H17, n-C12H25, and n-C18H37) strongly depends on the length of the hydrocarbon chain of the substituent R.
RESUMO
Intermetallic compounds with semiconducting properties are rare, but they give rise to advanced materials for energy conversion and saving applications. Here, we present ReGa2Ge, a new electron-precise narrow-gap intermetallic semiconductor. The compound crystallizes in the IrIn3 structure type (space group P42/mnm, a = 6.5734(3) Å, c = 6.7450(8) Å, and Z = 4), where Re atoms occupy the Ir site, while Ga and Ge jointly populate the In sites. 69,71Ga nuclear quadrupole resonance spectroscopy indicates nonstatistical partially ordered distribution of Ga and Ge over two available crystallographic sites; however, the Ga:Ge ratio is exactly 2:1 without noticeable homogeneity range. The stoichiometry of ReGa2Ge ensures its precise valence electron count, which is 17 e- per formula unit. Accordingly, a narrow energy gap opens up at the Fermi energy in the electronic structure. Electrical resistivity, Seebeck coefficient, and thermal conductivity are in agreement with the semiconducting behavior deduced from the electronic structure calculations and point to prospective thermoelectric properties at high temperatures. Bonding analysis reveals dominant covalency in Re-E (E = Ga, Ge) and Re-Re interactions.
RESUMO
ReGaGe2 is a new member of the family of intermetallic compounds with non-metallic properties. It displays highly localized covalent bonding patterns. Its electronic structure is governed by mixing of Re d orbitals with the s and p orbitals of Ga and Ge and features the Fermi level falling into the opened band gap, ensuring experimentally confirmed semiconducting properties.