Citation: CHI Yang, GUO Sheng-Ping. Syntheses and Crystal Structures of Two Al_xRE₃(Si_1-yAl_y)S₇ (RE = Sm and Gd) Compounds[J]. Chinese Journal of Structural Chemistry, ;2016, 35(3): 341-347. doi: 10.14102/j.cnki.0254-5861.2011-0978 shu

Syntheses and Crystal Structures of Two Al_xRE₃(Si_1-yAl_y)S₇ (RE = Sm and Gd) Compounds

CHI Yang ,
GUO Sheng-Ping ^,

1.
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China

Corresponding author: GUO Sheng-Ping,
Received Date: 16 September 2015
Available Online: 19 November 2015
Fund Project: This research was supported by the Higher Education Science Foundation of Jiangsu Province (No. 15KJB150031) (No. 15KJB150031) State Key Laboratory of Structural Chemistry (No. 20150009) (No. 20150009)

Two new quaternary rare-earth chalcogenides, Al_0.42Sm₃(Si_0.74Al_0.26)S₇ (1) and Al_0.38Gd₃(Si_0.86Al_0.14)S₇ (2), have been synthesized by a facile solid-state route with boron as the reducing reagent. They crystallize in the noncentrosymmetric hexagonal space group P6₃, belonging to the Ce₆Al_3.33S₁₄ structure-type. Their 3-D structures feature 3-D frameworks constructed by RES₈ bicapped trigonal prisms, and Al and Si occupy the octahedral and tetrahedral voids, respectively. Al(2) and Si(1) co-occupying the 2b site and Al(1) partially occupying the 2a site have to be considered for the stability of the structures and charge balances. The Ce₆Al_3.33S₁₄ structure-type compounds with their rich compositions and traits are discussed. The diffuse reflectance spectrum measurement of 2 indicates that it has an energy gap of 2.13 eV.
- rare-earth chalcogenides,
- solid-state reaction,
- crystal structure,
- energy gap
1. [1]
  (1) Mitchell, K.; Ibers, J. A. Rare-earth transition-metal chalcogenides. Chem. Rev. 2002, 102, 1929-1952.
2. [2]
  (2) Chung, I.; Kanatzidis, M. G. Metal chalcogenides: a rich source of nonlinear optical materials. Chem. Mater. 2014, 26, 849-869.
3. [3]
  (3) Hsu, K. F.; Loo, S.; Guo, F.; Chen, W.; Dyck, J. S.; Uher, C.; Hogan, T.; Polychroniadis, E. K.; Kanatzidis, M. G. Cubic AgPb_mSbTe_2+m: bulk thermoelectric materials with high figure of merit. Science 2004, 303, 818-821.
4. [4]
  (4) Sun, Y. Y.; Agiorgousis, M. L.; Zhang, P. H.; Zhang, S. B. Chalcogenide perovskites for photovoltaics. Nano Lett. 2015, 15, 581-585.
5. [5]
  (5) Li, H.; Malliakas, C. D.; Liu, Z. F.; Peters, J. A.; Sebastian, M.; Zhao, L. D.; Chung, D. Y.; Wessels, B. W.; Kanatzidis, M. G. Investigation of semi-insulating Cs₂Hg₆S₇ and Cs₂Hg_6-xCd_xS₇ alloy for hard radiation detection. Cryst. Growth & Des. 2014, 14, 5949-5956.
6. [6]
  (6) Guo, S. P.; Guo, G. C.; Wang, M. S.; Zou, J. P.; Xu, G.; Wang, G. J.; Long, X. F.; Huang, J. S. A series of new infrared NLO semiconductors, ZnY₆Si₂S₁₄, Al_xDy₃(Si_yAl_1-y)S₇, and Al_{0. 33}Sm₃SiS₇. Inorg. Chem. 2009, 48, 7059-7065.
7. [7]
  (7) Guo, S. P.; Zeng, H. Y.; Guo, G. C.; Zou, J. P.; Xu, G.; Huang, J. S. Syntheses, structures and band Gaps of KLnSiS₄(Ln = Sm, Yb). Chin. J. Struct. Chem. 2008, 27, 1543-1548.
8. [8]
  (8) Wei, F.; Wei, Z.; Chen, X. S.; Liu, G. B.; Cao, W. W.; Hu, P. A. Solid-state reaction synthesis of a InSe/CuInSe₂ lateral p-n heterojunction and application in high performance optoelectronic devices. Chem. Mater. 2015, 27, 983-989.
9. [9]
  (9) Ha, E.; Lee, L. Y. S.; Wang, J. C.; Li, F. H.; Wong, K. Y.; Tsang, S. C. E. Significant enhancement in photocatalytic reduction of water to hydrogen by Au/Cu₂ZnSnS₄ nanostructure. Adv. Mater. 2014, 26, 3496-3500.
10. [10]
  (10) Rudyk, B. W.; Stoyko, S. S.; Oliynyk, A. O.; Mar, A. Rare-earth transition-metal gallium chalcogenides RE₃MGaCh₇ (M = Fe, Co, Ni; Ch = S, Se). J. Solid State Chem. 2014, 210, 79-88.
11. [11]
  (11) Gulay, L. D.; Lychmanyuk, O. S.; Stępień-Damm, J.; Pietraszko, A.; Olekseyuk, I. D. Isothermal section of the Y₂S₃-Cu₂S-GeS₂ system at 870 K and crystal structures of the Y₃Ge_1.25S₇ and Y₃CuGeS₇ compounds. J. Alloys & Compd. 2006, 414, 113-117.
12. [12]
  (12) Zhao, H. J. Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE₃Sb_0.33SiS₇ (RE = La, Pr). J. Solid State Chem. 2015, 227, 5-9.
13. [13]
  (13) Huch, M. R.; Gulay, L. D.; Olekseyuk, I. D. Crystal structures of the R₃Mg_0.5GeS₇ (R = Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er) compounds. J. Alloys & Compd. 2006, 424, 114-118.
14. [14]
  (14) Guo, S. P.; Guo, G. C.; Wang, M. S.; Zou, J. P.; Zeng, H. Y.; Cai, L. Z.; Huang, J. S. A facile approach to hexanary chalcogenoborate featuring a 3-D chiral honeycomb-like open-framework constructed from rare-earth consolidating thiogallate-closo-dodecaborate. Chem. Commun. 2009, 29, 4366-4368.
15. [15]
  (15) Guo, S. P.; Wang, G. E.; Zhang, M. J.; Wu, M. F.; Liu, G. N.; Jiang, X. M.; Guo, G. C.; Huang, J. S. Novel single-crystal's voltage-dependent effect and magnetic order of Ln₂ZrQ₅ (Ln = La, Sm, Gd; Q = S, Se) semiconductors. Dalton Trans. 2013, 42, 2679-2682.
16. [16]
  (16) Guo, S. P.; Guo, G. C. Crystal structure and magnetic and photocatalytic properties of a new ternary rare-earth mixed chalcogenide, Dy₄S₄Te₃. J. Mater. Chem. A 2014, 2, 20621-20628.17.
17. [17]
  (17) Jiang, X. M.; Guo, S. P.; Zeng, H. Y.; Zhang, M. J.; Guo, G. C. Large crystal growth and new crystal exploration of mid-infrared second-order nonlinear optical materials. Struct. & Bond. 2012, 145, 1-43.
18. [18]
  (18) Rigaku, CrystalClear Version 1.3.5, Rigaku Corporation 2002.
19. [19]
  (19) Siemens, SHELXTLTM Version 5 Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA 1994.
20. [20]
  (20) Wendlandt, W. W.; Hecht, H. G. Reflectance Spectroscopy, Interscience Publishers, New York 1966.
21. [21]
  (21) Kortüm, G. Reflectance Spectroscopy, Springer 1969.
22. [22]
  (22) Pless, J. D.; Kim, H. S.; Smit, J. P.; Wang, X. D.; Stair, P. C.; Poeppelmeier, K. R. Structure of Mg_2.56V_1.12W_0.88O₈ and vibrational Raman spectra of Mg_2.5VWO₈ and Mg_2.5VMoO₈. Inorg. Chem. 2006, 45, 514-520.
23. [23]
  (23) Choi, K. S.; Chung, D. Y.; Mrotzek, A.; Brazis, P.; Kannewurf, C. R.; Uher, C.; Chen, W.; Hogan, T.; Kanatzidis, M. G. Modular construction of A_1+xM_4-2xM'_7+xSe₁₅ (A = K, Rb; M = Pb, Sn; M' = Bi, Sb): a new class of solid state quaternary thermoelectric compounds. Chem. Mater. 2001, 13, 756-764.
24. [24]
  (24) Mrotzek, A.; Kanatzidis, M. G. Tropochemical cell-twinning in the new quaternary bismuth selenides K_xSn_6-2xBi_2+xSe₉ and KSn₅Bi₅Se₁₃. Inorg. Chem. 2003, 42, 7200-7206.
25. [25]
  (25) Shi, Y. F.; Chen, Y. K.; Chen, M. C.; Wu, L. M.; Lin, H.; Zhou, L. J.; Chen, L. Strongest second harmonic generation in the polar R₃MTQ₇ family: atomic distribution induced nonlinear optical cooperation. Chem. Mater. 2015, 27, 1876-1884.
26. [26]
  (26) Choudhury, A.; Dorhout, P. K. Alkali-metal thiogermanates: sodium channels and variations on the La₃CuSiS₇ structure type. Inorg. Chem. 2015, 54, 1055-1065.
27. [27]
  (27) Lin, S. H.; Mao, J. G.; Guo, G. C.; Huang, J. S. Synthesis and crystal structure of a new quaternary compound: La₃AgSe₇Si. J. Alloy & Compd. 1997, 252, L8-L11.
28. [28]
  (28) Yin, W. L.; Shi, Y. G.; Kang, B.; Deng, J. G.; Yao, J. Y.; Wu, Y. C. Rare-earth transition-metal chalcogenides Ln₃MGaS₇ (Ln = Nd, Sm, Dy, Er; M = Co, Ni) and Ln₃MGaSe₇ (Ln = Nd, Sm, Gd, Dy, M = Co; Ln= Nd, Gd, Dy, M = Ni). J. Solid State Chem. 2014, 213, 87-92.
29. [29]
  (29) Yin, W. L.; Wang, W. D.; Kang, L.; Lin, Z. S.; Feng, K.; Shi, Y. G.; Hao, W. Y.; Yao, J. Y.; Wu, Y. C. Ln₃FeGaQ₇: a new series of transition-metal rare-earth chalcogenides. J. Solid State Chem. 2013, 202, 269-275.
30. [30]
  (30) Guo, S. P.; Zeng, H. Y.; Jiang, X. M.; Guo, G. C. Crystal structure and magnetic property of a quaternary sulfide, Al_0.36Sm₃Ge_0.98S₇. Chin. J. Struct. Chem. 2009, 11, 1448-1452.
31. [31]
  (31) Yang, Y. T.; Ibers, J. A. Accidental silicon-containing compounds: crystal structures of La₃Al_0.44Si_0.93S₇, BaSm₄(SiO₄)₃Se, and monoclinic and orthorhombic Ln₂(SiO₄)Te (Ln = Nd and Sm). J. Solid State Chem. 2000, 155, 433-440.
32. [32]
  (32) Zhao, Z. Y.; Liu, B. W.; Zeng, H. Y.; Jiang, X. M.; Zhang, M. J.; Zheng, F. K.; Guo, G. C. Syntheses and single-crystal structures of Ln₃Sn_0.25GeS₇ (Ln = La, Sm). Chin. J. Struct. Chem. 2012, 31, 1135-1139.
33. [33]
  (33) Daszkiewicz, M.; Gulay, L. D.; Lychmanyuk, O. S. Ln₃M_1-δTX₇-quasi-isostructural compounds: stereochemistry and silver-ion motion in the Ln₃Ag_1-δGeS₇ (Ln = La-Nd, Sm, Gd-Er and Y; _δ = 0.11～0.50) compounds. Acta Crystllogr. B 2009, 65, 126-133.
34. [34]
  (34) Patrie, M.; Guittard, M. Chimie minerale. Sur les composes du type Ce₆Al_10/3S₁₄. Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, Serie C, Sciences Chimiques 1969, 268, 1136-1138.
35. [35]
  (35) Iyer, A. K.; Rudyk, B. W.; Lin, X. S.; Singh, H.; Sharma, A. Z.; Wiebe, C. R.; Mar, A. Noncentrosymmetric rare-earth copper gallium chalcogenides RE₃CuGaCh₇ (RE = La-Nd; Ch = S, Se): an unexpected combination. J. Solid State Chem. 2015, 229, 150-159.
1. [1]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
2. [2]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
3. [3]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
4. [4]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
5. [5]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
6. [6]
  Huan ZHANG , Jijiang WANG , Guang FAN , Long TANG , Erlin YUE , Chao BAI , Xiao WANG , Yuqi ZHANG . A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 646-654. doi: 10.11862/CJIC.20230291
7. [7]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
8. [8]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
9. [9]
  Shuyan ZHAO . Field-induced Co^Ⅱ single-ion magnet with pentagonal bipyramidal configuration. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1583-1591. doi: 10.11862/CJIC.20240231
10. [10]
  Haodong Wang , Xiaoxu Lai , Chi Chen , Pei Shi , Houzhao Wan , Hao Wang , Xingguang Chen , Dan Sun . Novel 2D bifunctional layered rare-earth hydroxides@GO catalyst as a functional interlayer for improved liquid-solid conversion of polysulfides in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108473-. doi: 10.1016/j.cclet.2023.108473
11. [11]
  Hongdao LI , Shengjian ZHANG , Hongmei DONG . Magnetic relaxation and luminescent behavior in nitronyl nitroxide-based annuluses of rare-earth ions. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 972-978. doi: 10.11862/CJIC.20230411
12. [12]
  Biao Fang , Runwei Mo . PVDF-based solid-state battery. Chinese Journal of Structural Chemistry, 2024, 43(8): 100347-100347. doi: 10.1016/j.cjsc.2024.100347
13. [13]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
14. [14]
  Xinzhi Ding , Chong Liu , Jing Niu , Nan Chen , Shutao Xu , Yingxu Wei , Zhongmin Liu . Solid-state NMR study of the stability of MOR framework aluminum. Chinese Journal of Structural Chemistry, 2024, 43(4): 100247-100247. doi: 10.1016/j.cjsc.2024.100247
15. [15]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
16. [16]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
17. [17]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
18. [18]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
19. [19]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
20. [20]
  Peng Jia , Yunna Guo , Dongliang Chen , Xuedong Zhang , Jingming Yao , Jianguo Lu , Liqiang Zhang . In-situ imaging electrocatalysis in a solid-state Li-O₂ battery with CuSe nanosheets as air cathode. Chinese Chemical Letters, 2024, 35(5): 108624-. doi: 10.1016/j.cclet.2023.108624

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(875)
HTML views(38)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Syntheses and Crystal Structures of Two AlxRE3(Si1-yAly)S7 (RE = Sm and Gd) Compounds

Metrics

通讯作者: 陈斌, bchen63@163.com

Syntheses and Crystal Structures of Two Al_xRE₃(Si_1-yAl_y)S₇ (RE = Sm and Gd) Compounds