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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Synthesis of filled β-Mn-type ternary tellurides using a boron-tellurium reaction mixture
E A Chirantha Edirisinghe1, Subhendu Jana1, Eric A Gabilondo2
1Department of Chemistry and Biochemistry, Baylor University, Waco, TX, 76798, USA. Paul_Maggard@baylor.edu.
Abstract:
The synthetic discovery of new metal-telluride phases remains challenging due to the limitations of stabilizing increasingly complex compositions using conventional solid-state reactions. Described herein, a boron-tellurium mixture (BTM) reaction is demonstrated to provide an effective route to synthetically access ternary telluride phases within the alkali-triel-telluride (A-Tr-Te, A = alkali metal, Tr = Ga or In) compositional space. High quality single crystals and polycrystalline phases of the new NaIn3Te5 (1) and NaGa3Te5 (2) were prepared and structurally characterized by single crystal and powder X-ray diffraction techniques. These isostructural analogues crystallize in the noncentrosymmetric and chiral space group R32, exhibiting three-dimensionally condensed TrTe4 tetrahedra with a filled β-Mn-type network. Diffuse reflectance spectroscopy reveals that both are small bandgap semiconductors, with direct optical bandgaps of 1.18 eV and 0.79 eV for 1 and 2, respectively. Compound 1 exhibits a weak second-harmonic generation response under stimulation by a Ho:YAG laser at 2090 nm. Density functional theory calculations show that the valence band maximum is dominated by Te 5p states in both 1 and 2. Conversely, the conduction band states stem from mixed contributions of Tr and Te orbitals. These results provide the first experimental evaluation of the optical properties of the Na-Tr-Te (Tr = Ga, In) 1 : 3 : 5 telluride compounds, providing insights into the electronic structure and nonlinear optical properties of stuffed β-Mn-type telluride frameworks.
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