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. ^ a b 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. ^ a b 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. ^ a b 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. ^ a b 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. ^ a b c 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. ^ a b 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. ^ a b c d 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.
  • v
  • t
  • e
Arsenides
Binary arsenides
AsH3
+H 		He
LiAs Be BAs C +N +O F Ne
Na3As Mg AlAs -Si P S +Cl Ar
K CaAs Sc Ti V Cr MnAs Fe CoAs Ni Cu Zn3As2 GaAs -Ge As Se +Br Kr
Rb Sr YAs Zr Nb MoAs2 Tc Ru Rh PdAs2 Ag Cd3As2 InAs -Sn Sb +Te +I Xe
Cs Ba * Lu Hf TaAs WAs2 Re Os Ir Pt Au Hg Tl Pb BiAs Po At Rn
Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
* La Ce PrAs Nd Pm SmAs Eu Gd Tb Dy Ho Er Tm Yb
** Ac Th Pa U NpAs
NpAs2 		PuAs Am Cm Bk Cf Es Fm Md No
Ternary arsenidesQuaternary arsenidesQuinary arsenidesSee also
  • v
  • t
  • e
Salts and covalent derivatives of the silicide ion
SiH4
+H 		He
LiSi Be2Si SiB3
SiB6
+B 		SiC
+C 		Si3N4
-N
+N 		SiO2 SiF4 Ne
NaSi Mg2Si Al Si4− SiP, SiP2
-P
+P 		SiS2
-S 		SiCl4 Ar
KSi CaSi
CaSi2 		ScSi Sc5Si3 Sc2Si3 Sc5Si4 TiSi
TiSi2 		V3Si V5Si3, V6Si5, VSi2, V6Si5 Cr3Si Cr5Si3, CrSi, CrSi2 MnSi, MnSi2, Mn9Si2, Mn3Si, Mn5Si3, Mn11Si9 FeSi2
FeSi
Fe5Si3
Fe2Si
Fe3Si 		CoSi, CoSi2, Co2Si, Co3Si NiSi, more… Cu17Si3, Cu56Si11, Cu5Si, Cu33Si7, Cu4Si, Cu19Si6, Cu3Si, Cu87Si13 Zn Ga GeSi
+Ge 		SiAs, SiAs2
-As
+As 		SiSe2 SiSe SiBr4 Kr
RbSi SrSi2 YSi Y5Si3, Y5Si4, Y3Si5, YSi1.4 ZrSi Zr5Si3, Zr5Si4, ZrSi2, Zr3Si2, Zr2Si, Zr3Si Nb4Si Nb5Si3 MoSi2
Mo3Si Mo5Si3 		Tc RuSi Ru2Si, Ru4Si3, Ru2Si3 RhSi Rh2Si, Rh5Si3, Rh3Si2, Rh20Si13 PdSi Pd5Si, Pd9Si2, Pd3Si, Pd2Si Ag Cd In Sn Sb TeSi2 Te2Si3 SiI4 Xe
CsSi Ba2Si BaSi2, Ba5Si3 Ba3Si4 * Lu5Si3 HfSi Hf2Si, Hf3Si2, Hf5Si4, HfSi2 Ta9Si2, Ta3Si, Ta5Si3 WSi2 W5Si3 ReSi Re2Si, ReSi1.8 Re5Si3 OsSi IrSi PtSi Au Hg Tl Pb Bi Po At Rn
Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaSi2 La5Si3, La3Si2, La5Si4, LaSi CeSi2 Ce5Si3, Ce3Si2, Ce5Si4, CeSi, Ce3Si5 PrSi2 Pr5Si3, Pr3Si2, Pr5Si4, PrSi NdSi Nd5Si3, Nd5Si4, Nd5Si3, Nd3Si4, Nd2Si3, NdSix Pm SmSi2 Sm5Si4, Sm5Si3, SmSi, Sm3Si5 Eu? GdSi2 Gd5Si3, Gd5Si4, GdSi TbSi2 SiTb, Si4Tb5, Si3Tb5 DySi2 DySi HoSi2 Ho5Si3, Ho5Si4, HoSi, Ho4Si5 ErSi2 Er5Si3, Er5Si4, ErSi Tm? YbSi Si1.8Yb, Si5Yb3, Si4Yb3, Si4Yb5, Si3Yb5
** Ac ThSi PaSi USi2 NpSi2 PuSi Am Cm Bk Cf Es Fm Md No