Quaternary Supertetrahedra-Layered Telluride CsMnInTe₃: Why Does This Type of Chalcogenide Tilt?

Dark-red CsMnInTe₃ is synthesized by a solid-state approach using CsCl as the reactive flux. This layered compound is constructed by T₃ supertetrahedra and crystallizes in the space group <i>C</i>2/<i>c</i> with <i>a</i> = 12.400(7) Å, <i>b</i> = 12.400(7) Å, <i>c</i> = 24.32(2) Å, β = 97.31(2)°, and <i>V</i> = 927.07(6) ų. The electrostatic interactions cause tilting of the supertetrahedra layers, and the value of the tilting angle is fixed by a structure index, β′ = 180° – arccos­(<i>a</i>/4<i>c</i>). Such an index is valid for all of the members in this family known to date

A Ferrimagnetic Zintl Phase Pr₄MnSb₉: Synthesis, Structure, and Physical Properties

A new valence precise Zintl phase, Pr₄MnSb₉, has been successfully synthesized by solid-state reaction at high temperature. The single-crystal X-ray diffraction data reveal its monoclinic symmetry in the space group <i>C</i>2/<i>m</i> (No. 12) with <i>a</i> = 24.12(2) Å, <i>b</i> = 4.203(3) Å, <i>c</i> = 15.67(2) Å, β = 98.05(1)°, and <i>Z</i> = 4. The structure is characterized by the covalent three-dimensional network constructed by two types of five-atom-wide Sb₅^7– ribbons that are joined by 6-fold coordinated Mn³⁺ cations, through which the narrower three-atom-wide Sb₃^5– ribbons are attached as a tag, and interstitial Pr³⁺ cations and single Sb^3– anions locate within the tunnels. Its magnetic susceptibility and isothermal hysteresis suggest ferrimagnetic behavior. The electrical conductivity and Seebeck coefficient of the cold-pressed pellet suggest a semimetal feature that agrees with the spin-polarized calculation results using the tight-binding linear muffin-tin orbital (TB-LMTO) method

A Ferrimagnetic Zintl Phase Pr₄MnSb₉: Synthesis, Structure, and Physical Properties

A new valence precise Zintl phase, Pr₄MnSb₉, has been successfully synthesized by solid-state reaction at high temperature. The single-crystal X-ray diffraction data reveal its monoclinic symmetry in the space group <i>C</i>2/<i>m</i> (No. 12) with <i>a</i> = 24.12(2) Å, <i>b</i> = 4.203(3) Å, <i>c</i> = 15.67(2) Å, β = 98.05(1)°, and <i>Z</i> = 4. The structure is characterized by the covalent three-dimensional network constructed by two types of five-atom-wide Sb₅^7– ribbons that are joined by 6-fold coordinated Mn³⁺ cations, through which the narrower three-atom-wide Sb₃^5– ribbons are attached as a tag, and interstitial Pr³⁺ cations and single Sb^3– anions locate within the tunnels. Its magnetic susceptibility and isothermal hysteresis suggest ferrimagnetic behavior. The electrical conductivity and Seebeck coefficient of the cold-pressed pellet suggest a semimetal feature that agrees with the spin-polarized calculation results using the tight-binding linear muffin-tin orbital (TB-LMTO) method

Syntheses, Characterization, and Optical Properties of Centrosymmetric Ba₃(BS₃)_1.5(MS₃)_0.5 and Noncentrosymmetric Ba₃(BQ₃)(SbQ₃)

The most advanced UV–vis and IR NLO materials are usually borates and chalcogenides, respectively. But thioborates, especially thio-borometalates, are extremely rare. Here, four new such compounds are discovered by solid state reactions representing 0D structures constructed by isolated BQ₃ trigonal planes and discrete MQ₃ pyramids with Ba²⁺ cations filling among them, centrosymmetric monoclinic <i>P</i>2₁<i>/c</i> Ba₃(BS₃)_1.5(MS₃)_0.5 (M = Sb, Bi) <b>1</b>, <b>2</b> with <i>a</i> = 12.9255(9), 12.946(2) Å; <i>b</i> = 21.139(2), 21.170(2)­Å; <i>c</i> = 8.4194(6), 8.4207(8) Å; β = 101.739(5), 101.688(7)°; <i>V</i> = 2252.3(3), 2259.9(3) ų and noncentrosymmetric hexagonal <i>P</i>6̅2<i>m</i> Ba₃(BQ₃)­(SbQ₃) (Q = S, Se) <b>3</b>, <b>4</b> with <i>a</i> = <i>b</i> = 17.0560(9), 17.720(4) Å; <i>c</i> = 10.9040(9), 11.251(3) Å; <i>V</i> = 2747.1(3), 3060(2) ų. <b>3</b> exhibits the strongest SHG among thioborates that is about three times that of the benchmark AgGaS₂ at 2.05 μm. <b>1</b> and <b>3</b> also show an interesting structure relationship correlated to the size mismatching of the anionic building units that can be controlled by the experimental loading ratio of B:Sb. Syntheses, structure characterizations, and electronic structures based on the density functional theory calculations are reported