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
Li2 SiAs2
tetragonal
I 41 /acd
a =12.563 c =19.390
red; air sensitive; Si4 As10 units
[ 1]
LiSi3 As6
orthorhombic
Cmca
a =14.244 b =11.247 c =10.757
water and acid stable
[ 1]
Li5 SiAs3
C 2/c
black, hydrolysed by water
[ 2]
Li3 Si7 As8
monoclinic
P 2/m
a=8.9904 b=3.7154 c=11.6023 β=96.307 Z=1
385.21
3.52
layered; moisture sensitive
[ 3]
NaSi3 As3
a=10.002 b=18.54 c=3.648
[ 4]
MgSiAs2
202.24
I 4 2d
a=5.9078 c=10.600 Z=4
369.96
3.63
[ 5]
Mg3 Si6 As8
840.33
cubic
P43 32
a=11.600 Z=4
1560.9
3.58
red
[ 5]
K2 SiAs2
Ibam
a=13.132 b=6.999 c=6.340 Z=4
golden; explosive decomposition; air sensitive; CAS No=108945-44-4
[ 6]
KSi3 As3
Pbam
a=10.010b=19.139 c=3.664 Z=4
purple; 2D framework
[ 4]
Sr3 Si2 As4
metallic red; chains
[ 7]
CdSiAs2
tetragonal
I 4 2d
a = 5.884 c = 10.882 Z=8
[ 8] [ 9]
Cd7 SiAs6
1264.41
cubic
P21 3
a=10.9820 Z=4
1324.5
6.343
black
[ 8]
Cs0.16 SiAs2
water stable
[ 10]
Cs2 SiAs2
orthorhombic
Ibam
a=7.571 b=14.425 c=6.42
water sensitive
[ 10] [ 11]
Cs5 SiAs3
orthorhombic
Pnma
a=14.467 b=6.043 c=15.82
dark red metallic; air sensitive; planar
[ 10] [ 11]
Cs0.11 Zn0.05 Si0.95 As
119.39
monoclinic
C 2/m
a=35.201 b=3.6649 c=9.9848 β=91.863° Z=24
1287.4
3.70
black
[ 12]
Ba4 SiAs4
dark metallic; unstable in air
[ 13]
BaCuSi2 As3
P n m a
a 13.169 b 10.502 c 4.615
thermal insulate, electrical conductor
[ 14]
Ba13 Si6 Sn8 As22
4551.72
tetragonal
I 4 2m
a = 14.4857, c = 13.5506 Z=2
2843.4
5.316
black; Si4 As10 units; band gap 1.0 eV
[ 15]
LaSiAs3
orthorhombic
Pbca
a=6.0855 b=5.9837 c=26.2279 Z=8
[ 16]
LaSiAs3
orthorhombic
Pn 21 a
a=6.0498 b=5.9545 c=26.383 Z=8
[ 16]
CeSiAs3
orthorhombic
Pn 21 a
a=5.998 b=5.906 c=26.231 Z=8
[ 16]
PrSiAs3
orthorhombic
Pn 21 a
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
^ 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 .
^ 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 .
^ 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 .
^ 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 .
^ 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 .
^ 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 .
^ 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 .
^ 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 .
^ "MatWeb – The Online Materials Information Resource" . www.matweb.com . Retrieved 2021-12-08 .
^ 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 .
^ 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 .
^ 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 . OSTI 1798868 . S2CID 236258955 .
^ 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 .
^ 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 . OSTI 1777937 . PMID 33794094 . S2CID 232762736 .
^ 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 .
^ 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 .
^ 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 .
Salts and covalent derivatives of the
silicide ion
SiH4 +H
He
LiSi
Be2 Si
SiB3 SiB6 +B
SiC +C
Si3 N4 -N +N
SiO2
SiF4
Ne
NaSi
Mg2 Si
Al
Si4−
SiP, SiP2 -P +P
SiS2 -S
SiCl4
Ar
KSi
CaSi CaSi2
ScSi Sc5 Si3 Sc2 Si3 Sc5 Si4
TiSi TiSi2
V3 Si V5 Si3 , V6 Si5 , VSi2 , V6 Si5
Cr3 Si Cr5 Si3 , CrSi, CrSi2
MnSi , MnSi2 , Mn9 Si2 , Mn3 Si, Mn5 Si3 , Mn11 Si9
FeSi2 FeSi Fe5 Si3 Fe2 Si Fe3 Si
CoSi , CoSi2 , Co2 Si , Co3 Si
NiSi , more…
Cu17 Si3 , Cu56 Si11 , Cu5 Si, Cu33 Si7 , Cu4 Si, Cu19 Si6 , Cu3 Si, Cu87 Si13
Zn
Ga
GeSi +Ge
SiAs, SiAs2 -As +As
SiSe2 SiSe
SiBr4
Kr
RbSi
SrSi2
YSi Y5 Si3 , Y5 Si4 , Y3 Si5 , YSi1.4
ZrSi Zr5 Si3 , Zr5 Si4 , ZrSi2 , Zr3 Si2 , Zr2 Si, Zr3 Si
Nb4 Si Nb5 Si3
MoSi2 Mo3 Si Mo5 Si3
Tc
RuSi Ru2 Si, Ru4 Si3 , Ru2 Si3
RhSi Rh2 Si, Rh5 Si3 , Rh3 Si2 , Rh20 Si13
PdSi Pd5 Si, Pd9 Si2 , Pd3 Si, Pd2 Si
Ag
Cd
In
Sn
Sb
TeSi2 Te2 Si3
SiI4
Xe
CsSi
Ba2 Si BaSi2 , Ba5 Si3 Ba3 Si4
*
Lu5 Si3
HfSi Hf2 Si, Hf3 Si2 , Hf5 Si4 , HfSi2
Ta9 Si2 , Ta3 Si, Ta5 Si3
WSi2 W5 Si3
ReSi Re2 Si, ReSi1.8 Re5 Si3
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 La5 Si3 , La3 Si2 , La5 Si4 , LaSi
CeSi2 Ce5 Si3 , Ce3 Si2 , Ce5 Si4 , CeSi , Ce3 Si5
PrSi2 Pr5 Si3 , Pr3 Si2 , Pr5 Si4 , PrSi
NdSi Nd5 Si3 , Nd5 Si4 , Nd5 Si3 , Nd3 Si4 , Nd2 Si3 , NdSix
Pm
SmSi2 Sm5 Si4 , Sm5 Si3 , SmSi, Sm3 Si5
Eu?
GdSi2 Gd5 Si3 , Gd5 Si4 , GdSi
TbSi2 SiTb, Si4 Tb5 , Si3 Tb5
DySi2 DySi
HoSi2 Ho5 Si3 , Ho5 Si4 , HoSi, Ho4 Si5
ErSi2 Er5 Si3 , Er5 Si4 , ErSi
Tm?
YbSi Si1.8 Yb, Si5 Yb3 , Si4 Yb3 , Si4 Yb5 , Si3 Yb5
**
Ac
ThSi
PaSi
USi2
NpSi2
PuSi
Am
Cm
Bk
Cf
Es
Fm
Md
No