Arsenidosilicate

Arsenidosilicates are chemical compounds that contain anions with arsenic bonded to silicon. They are in the category of tetrelarsenides, pnictidosilicates, or tetrelpnictides. They can be classed as Zintl phases or intermetallics. They are analogous to the nitridosilicates, phosphidosilicates, arsenidogermanates, and arsenidostannates. They are distinct from arsenate silicates which have oxygen connected with arsenic and silicon, or arsenatosilicates with arsenate groups sharing oxygen with silicate.

Arsenidosilicates have dark coloured crystals, usually metallic black. They are often decomposed by water, and some are unstable with respect to the water in air.

These compounds have been investigated as ionic conductors, semiconductors and photovoltaics.

List
name formula formula

weight

 crystal

system

 space

group

 unit cell volume density comments ref
Li2SiAs2 tetragonal I41/acd a=12.563 c=19.390 red; air sensitive; Si4As10 units [1]
LiSi3As6 orthorhombic Cmca a=14.244 b=11.247 c=10.757 water and acid stable [1]
Li5SiAs3 C2/c black, hydrolysed by water [2]
Li3Si7As8 monoclinic P2/m a=8.9904 b=3.7154 c=11.6023 β=96.307 Z=1 385.21 3.52 layered; moisture sensitive [3]
NaSi3As3 a=10.002 b=18.54 c=3.648 [4]
MgSiAs2 202.24 I42d a=5.9078 c=10.600 Z=4 369.96 3.63 [5]
Mg3Si6As8 840.33 cubic P4332 a=11.600 Z=4 1560.9 3.58 red [5]
K2SiAs2 Ibam a=13.132 b=6.999 c=6.340 Z=4 golden; explosive decomposition; air sensitive; CAS No=108945-44-4 [6]
KSi3As3 Pbam a=10.010b=19.139 c=3.664 Z=4 purple; 2D framework [4]
Sr3Si2As4 metallic red; chains [7]
CdSiAs2 tetragonal I42d a = 5.884 c = 10.882 Z=8 [8][9]
Cd7SiAs6 1264.41 cubic P213 a=10.9820 Z=4 1324.5 6.343 black [8]
Cs0.16SiAs2 water stable [10]
Cs2SiAs2 orthorhombic Ibam a=7.571 b=14.425 c=6.42 water sensitive [10][11]
Cs5SiAs3 orthorhombic Pnma a=14.467 b=6.043 c=15.82 dark red metallic; air sensitive; planar [10][11]
Cs0.11Zn0.05Si0.95As 119.39 monoclinic C2/m a=35.201 b=3.6649 c=9.9848 β=91.863° Z=24 1287.4 3.70 black [12]
Ba4SiAs4 dark metallic; unstable in air [13]
BaCuSi2As3 P n m a a 13.169 b 10.502 c 4.615 thermal insulate, electrical conductor [14]
Ba13Si6Sn8As22 4551.72 tetragonal I42m a = 14.4857, c = 13.5506 Z=2 2843.4 5.316 black; Si4As10 units; band gap 1.0 eV [15]
LaSiAs3 orthorhombic Pbca a=6.0855 b=5.9837 c=26.2279 Z=8 [16]
LaSiAs3 orthorhombic Pn21a a=6.0498 b=5.9545 c=26.383 Z=8 [16]
CeSiAs3 orthorhombic Pn21a a=5.998 b=5.906 c=26.231 Z=8 [16]
PrSiAs3 orthorhombic Pn21a a = 5.949, b = 5.877, c = 26.149 Z=8 [16]
AuSiAs monoclinic Cc a 7.2000 b 6.1614 c 6.1646, β =119.135° [17]

References
  1. Mark, Justin; Lee, Kathleen; Marple, Maxwell A. T.; Lee, Shannon; Sen, Sabyasachi; Kovnir, Kirill (2020). "LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity". Journal of Materials Chemistry A. 8 (6): 3322–3332. doi:10.1039/C9TA11150F. ISSN 2050-7488. S2CID 214001466.
  2. Juza, Robert; Schulz, Werner (February 1954). "Ternäre Phosphide und Arsenide des Lithiums mit Elementen der 3. und 4. Gruppe". Zeitschrift für anorganische und allgemeine Chemie (in German). 275 (1–3): 65–78. doi:10.1002/zaac.19542750107. ISSN 0044-2313.
  3. Mark, Justin; Hanrahan, Michael P.; Woo, Katherine E.; Lee, Shannon; Rossini, Aaron J.; Kovnir, Kirill (2019-05-02). "Chemical and Electrochemical Lithiation of van der Waals Tetrel‐Arsenides". Chemistry – A European Journal. 25 (25): 6392–6401. doi:10.1002/chem.201900339. ISSN 0947-6539. OSTI 1526289. PMID 30887569. S2CID 83463348.
  4. Hurng, Weir Mirn; Corbett, John D.; Wang, Sue Lein; Jacobson, Robert A. (July 1987). "A Zintl phase with a layered network structure, potassium silicon arsenide (KSi3As3)". Inorganic Chemistry. 26 (15): 2392–2395. doi:10.1021/ic00262a012. ISSN 0020-1669.
  5. Woo, Katherine E.; Wang, Jian; Wu, Kui; Lee, Kathleen; Dolyniuk, Juli‐Anna; Pan, Shilie; Kovnir, Kirill (July 2018). "MgSiAs: An Unexplored System with Promising Nonlinear Optical Properties". Advanced Functional Materials. 28 (30): 1801589. doi:10.1002/adfm.201801589. ISSN 1616-301X. S2CID 104074348.
  6. Hurng, Weir Mirn; Peterson, Eric S.; Corbett, John D. (November 1989). "Synthesis and structure of the Zintl phase potassium silicon arsenide, K2SiAs2". Inorganic Chemistry. 28 (22): 4177–4180. doi:10.1021/ic00321a029. ISSN 0020-1669.
  7. Eisenmann, Brigitte; Schäfer, Herbert (June 1980). "Zintl Phases with Complex Anions: Sr 3 Si 2 As 4 and Sr 3 Ge 2 As 4". Angewandte Chemie International Edition in English. 19 (6): 490–491. doi:10.1002/anie.198004901.
  8. Li, Chunxiao; Liu, Youquan; Liu, Wenhao; Liu, Juhe; Meng, Xianghe; Lin, Zheshuai; Yao, Jiyong (2 December 2021). "Cd 7 SiAs 6 , a Nonchalcopyrite Arsenide with a Strong Nonlinear-Optical Response". Inorganic Chemistry. 60 (24): 18634–18638. doi:10.1021/acs.inorgchem.1c03446. PMID 34854683. S2CID 244800044.
  9. "MatWeb – The Online Materials Information Resource". www.matweb.com. Retrieved 2021-12-08.
  10. Eisenmann, Brigitte; Klein, Jürgen; Somer, Mehmet (January 1990). "Anions Isosteric with CO32− in Cs5SiP3, Cs5SiAs3, Cs5GeP3, and Cs5GeAs3". Angewandte Chemie International Edition in English. 29 (1): 87–88. doi:10.1002/anie.199000871. ISSN 0570-0833.
  11. Villars, Pierre; Cenzual, Karin; Gladyshevskii, Roman (2017-07-24). Handbook. Walter de Gruyter GmbH & Co KG. p. 859. ISBN 978-3-11-043655-6.
  12. Mark, Justin; Woo, Katherine E.; Zhu, Weidi; Ji, Bingheng; Lee, Shannon J.; Adeyemi, Adedoyin N.; Sen, Sabyasachi; Kovnir, Kirill (2021-06-22). "Two-Dimensional and Three-Dimensional Tetrel-Arsenide Frameworks Templated by Li and Cs Cations". Chemistry of Materials. 33 (12): 4586–4595. doi:10.1021/acs.chemmater.1c01053. ISSN 0897-4756. S2CID 236258955.
  13. Eisenmann, Brigitte; Jordan, Hanna; Schäfer, Herbert (February 1981). "Ba4SiAs4, and Ba4GeAs4, Zintl Phases with Isolated SiAs48− and GeAs48− anions". Angewandte Chemie International Edition in English. 20 (2): 197–198. doi:10.1002/anie.198101972. ISSN 0570-0833.
  14. Yox, Philip; Lee, Shannon J.; Wang, Lin-lin; Jing, Dapeng; Kovnir, Kirill (2021-04-19). "Crystal Structure and Properties of Layered Pnictides BaCuSi 2 Pn 3 (Pn = P, As)". Inorganic Chemistry. 60 (8): 5627–5634. doi:10.1021/acs.inorgchem.0c03636. ISSN 0020-1669. PMID 33794094. S2CID 232762736.
  15. Liu, Xiao-Cun; Lin, Na; Wang, Jian; Pan, Ming-Yan; Zhao, Xian; Tao, Xu-Tang; Xia, Sheng-Qing (2013-10-21). "Ba 13 Si 6 Sn 8 As 22 : A Quaternary Zintl Phase Containing Adamantane-Like [Si 4 As 10 ] Clusters". Inorganic Chemistry. 52 (20): 11836–11842. doi:10.1021/ic402023z. ISSN 0020-1669. PMID 24079277.
  16. Hayakawa, H; Ono, S (December 1988). "Studies on syntheses and conditions of formation for LnSiAs3 compounds (Ln ≡ La, Ce, Pr)". Journal of the Less Common Metals. 144 (2): 177–194. doi:10.1016/0022-5088(88)90130-0.
  17. Lee, Shannon J.; Won, Juyeon; Wang, Lin‐Lin; Jing, Dapeng; Harmer, Colin P.; Mark, Justin; Akopov, Georgiy; Kovnir, Kirill (2021-05-06). "New Noncentrosymmetric Tetrel Pnictides Composed of Square‐Planar Gold(I) with Peculiar Bonding". Chemistry – A European Journal. 27 (26): 7383–7390. doi:10.1002/chem.202005312. ISSN 0947-6539. PMC 8251799. PMID 33523500.
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