More Like this

1. Chemically driven superstructural ordering leading to giant unit cells in unconventional clathrates Cs ₈ Zn ₁₈ Sb ₂₈ and Cs ₈ Cd ₁₈ Sb ₂₈

   https://doi.org/10.1039/D0SC03846F  

   Owens-Baird, Bryan ; Yox, Philip ; Lee, Shannon ; Carroll, Xian B. ; Grass Wang, Suyin ; Chen, Yu-Sheng ; Lebedev, Oleg I. ; Kovnir, Kirill ( September 2020 , Chemical Science)

   The unconventional clathrates, Cs 8 Zn 18 Sb 28 and Cs 8 Cd 18 Sb 28 , were synthesized and reinvestigated. These clathrates exhibit unique and extensive superstructural ordering of the clathrate-I structure that was not initially reported. Cs 8 Cd 18 Sb 28 orders in the Ia 3̄ d space group (no. 230) with 8 times larger volume of the unit cell in which most framework atoms segregate into distinct Cd and Sb sites. The structure of Cs 8 Zn 18 Sb 28 is much more complicated, with an 18-fold increase of unit cell volume accompanied by significant reduction of symmetry down to P 2 (no. 3) monoclinic space group. This structure was revealed by a combination of synchrotron X-ray diffraction and electron microscopy techniques. A full solid solution, Cs 8 Zn 18−x Cd x Sb 28 , was also synthesized and characterized. These compounds follow Vegard's law in regard to their primitive unit cell sizes and melting points. Variable temperature in situ synchrotron powder X-ray diffraction was used to study the formation and melting of Cs 8 Zn 18 Sb 28 . Due to the heavy elements comprising clathrate framework and the complex structural ordering, the synthesized clathratesmore »exhibit ultralow thermal conductivities, all under 0.8 W m −1 K −1 at room temperature. Cs 8 Zn 9 Cd 9 Sb 28 and Cs 8 Zn 4.5 Cd 13.5 Sb 28 both have total thermal conductivities of 0.49 W m −1 K −1 at room temperature, among the lowest reported for any clathrate. Cs 8 Zn 18 Sb 28 has typical p-type semiconducting charge transport properties, while the remaining clathrates show unusual n–p transitions or sharp increases of thermopower at low temperatures. Estimations of the bandgaps as activation energy for resistivity dependences show an anomalous widening and then shrinking of the bandgap with increasing Cd-content.« less
2. Crystal Growth of New Germanate Framework Structures: Impact of the Presence of Square Planar Copper Species and Mixed Ge/Mn Sites on the Overall Structures of Rb ₂ Cu ₃ Ge ₅ O ₁₄ , Cs ₂ Cu ₃ Ge ₅ O ₁₄ , Cs ₇ Cu ₂ Ge ₁₁ O ₂₇ F, and [(Cs ₆ F)(Cs ₃ AgF)][Ge ₁₂ Mn ₂ O ₃₂ ]

   https://doi.org/10.1021/acs.cgd.2c00133  

   Carone, Darren ; Morrison, Gregory ; Smith, Mark D. ; zur Loye, Hans-Conrad ( May 2022 , Crystal Growth & Design)
3. Structure and Bonding in [Sb@In ₈ Sb ₁₂ ] ³⁻ and [Sb@In ₈ Sb ₁₂ ] ⁵⁻

   https://doi.org/10.1002/anie.201904109  

   Liu, Chao ; Tkachenko, Nikolay V. ; Popov, Ivan A. ; Fedik, Nikita ; Min, Xue ; Xu, Cong-Qiao ; Li, Jun ; McGrady, John E. ; Boldyrev, Alexander I. ; Sun, Zhong-Ming ( June 2019 , Angewandte Chemie International Edition)
4. Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB ₃ H ₈ (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB ₃ H ₈

   https://doi.org/10.1002/anie.201812795  

   Chen, Xi-Meng ; Ma, Nana ; Liu, Xin-Ran ; Wei, Changgeng ; Cui, Chong-Chao ; Cao, Bu-La ; Guo, Yanhui ; Wang, Lai-Sheng ; Gu, Qinfen ; Chen, Xuenian ( February 2019 , Angewandte Chemie International Edition)
5. High-efficiency blue photoluminescence in the Cs ₂ NaInCl ₆ :Sb ³⁺ double perovskite phosphor

   https://doi.org/10.1039/D0TC01037E  

   Gray, Matthew B. ; Hariyani, Shruti ; Strom, T. Amanda ; Majher, Jackson D. ; Brgoch, Jakoah ; Woodward, Patrick M. ( May 2020 , Journal of Materials Chemistry C)

   In this paper, the photoluminescent properties of a lead-free double perovskite Cs 2 NaInCl 6 doped with Sb 3+ are explored. The host crystal structure is a cubic double perovskite with Fm 3̄ m symmetry, a = 10.53344(4) Å, and rock salt ordering of Na + and In 3+ . It is a wide bandgap compound ( E g ≈ 5.1 eV), and substitution with Sb 3+ leads to strong absorption in the UV due to localized 5s 2 → 5s 1 5p 1 transitions on Sb 3+ centers. Radiative relaxation back to the 5s 2 ground state, via a 3 P 1 → 1 S 0 transition, leads to intense blue luminescence, centered at 445 nm, with a photoluminescent quantum yield of 79%. The Stokes shift of 0.94 eV is roughly 33% smaller than it is in the related vacancy ordered double perovskite Cs 2 SnCl 6 . The reduction in Stokes shift is likely due to a change in coordination number of Sb 3+ from 6-coordinate in Cs 2 NaInCl 6 to 5-coordinate in Cs 2 SnCl 6 . In addition to the high quantum yield, Cs 2 NaInCl 6 :Sb 3+ exhibits excellent air/moisture stability and canmore »be prepared from solution; these characteristics make it a promising blue phosphor for applications involving near-UV excitation.« less