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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)

   null (Ed.)

   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 clathrates 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. 

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2. 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)
3. Transformation of K ₂ Sb ₈ Q ₁₃ and KSb ₅ Q ₈ Bulk Crystals to Sb ₂ Q ₃ (Q = S, Se) Nanofibers by Acid–Base Solution Chemistry

   https://doi.org/10.1021/jacs.3c03925  

   Lee, Hyungseok; Yoo, Byeongjun; Kim, Dawoon; Cha, Joonil; Kang, Yeo Kyung; Cho, Sung-Pyo; Hyeon, Taeghwan; Kim, Myung-Gil; Kanatzidis, Mercouri G.; Chung, In (July 2023, Journal of the American Chemical Society)
4. The impact of site selectivity and disorder on the thermoelectric properties of Yb ₂₁ Mn ₄ Sb ₁₈ solid solutions: Yb ₂₁ Mn _4−x Cd _x Sb ₁₈ and Yb _21−y Ca _y Mn ₄ Sb ₁₈

   https://doi.org/10.1039/d1ma00497b  

   He, Allan; Cerretti, Giacomo; Kauzlarich, Susan M. (August 2021, Materials Advances)

   Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca are isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K. 

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5. A InSn ₂ S ₆ ( A = K, Rb, Cs)─Layered Semiconductors Based on the SnS ₂ Structure

   https://doi.org/10.1021/acs.inorgchem.2c02157  

   Friedrich, Daniel; Quintero, Michael A.; Hao, Shiqiang; Laing, Craig C.; Wolverton, Christopher; Kanatzidis, Mercouri G. (August 2022, Inorganic Chemistry)