Arsenidosilicate

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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

nameformulaformula

weight

crystal

system

space

group

unit cellvolumedensitycommentsref
Li2SiAs2tetragonalI41/acda=12.563 c=19.390red; air sensitive; Si4As10 units [1]
LiSi3As6orthorhombicCmcaa=14.244 b=11.247 c=10.757water and acid stable [1]
Li5SiAs3C2/cblack, hydrolysed by water [2]
Li3Si7As8monoclinicP2/ma=8.9904 b=3.7154 c=11.6023 β=96.307 Z=1385.213.52layered; moisture sensitive [3]
NaSi3As3a=10.002 b=18.54 c=3.648 [4]
MgSiAs2202.24I42da=5.9078 c=10.600 Z=4369.963.63 [5]
Mg3Si6As8840.33cubicP4332a=11.600 Z=41560.93.58red [5]
K2SiAs2Ibama=13.132 b=6.999 c=6.340 Z=4golden; explosive decomposition; air sensitive; CAS No=108945-44-4 [6]
KSi3As3Pbama=10.010b=19.139 c=3.664 Z=4purple; 2D framework [4]
Sr3Si2As4metallic red; chains [7]
CdSiAs2tetragonalI42da = 5.884 c = 10.882 Z=8 [8] [9]
Cd7SiAs61264.41cubicP213a=10.9820 Z=41324.56.343black [8]
Cs0.16SiAs2water stable [10]
Cs2SiAs2orthorhombicIbama=7.571 b=14.425 c=6.42water sensitive [10] [11]
Cs5SiAs3orthorhombicPnmaa=14.467 b=6.043 c=15.82dark red metallic; air sensitive; planar [10] [11]
Cs0.11Zn0.05Si0.95As119.39monoclinicC2/ma=35.201 b=3.6649 c=9.9848 β=91.863° Z=241287.43.70black [12]
Ba4SiAs4dark metallic; unstable in air [13]
BaCuSi2As3P n m aa 13.169 b 10.502 c 4.615thermal insulate, electrical conductor [14]
Ba13Si6Sn8As224551.72tetragonalI42ma = 14.4857, c = 13.5506 Z=22843.45.316black; Si4As10 units; band gap 1.0 eV [15]
LaSiAs3orthorhombicPbcaa=6.0855 b=5.9837 c=26.2279 Z=8 [16]
LaSiAs3orthorhombicPn21aa=6.0498 b=5.9545 c=26.383 Z=8 [16]
CeSiAs3orthorhombicPn21aa=5.998 b=5.906 c=26.231 Z=8 [16]
PrSiAs3orthorhombicPn21aa = 5.949, b = 5.877, c = 26.149 Z=8 [16]
AuSiAsmonoclinicCca 7.2000 b 6.1614 c 6.1646, β =119.135° [17]

Related Research Articles

In chemistry, a Zintl phase is a product of a reaction between a group 1 or group 2 and main group metal or metalloid. It is characterized by intermediate metallic/ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors.

The phosphidosilicates or phosphosilicides are inorganic compounds containing silicon bonded to phosphorus and one or more other kinds of elements. In the phosphosilicates each silicon atom is surrounded by four phosphorus atoms in a tetrahedron. The triphosphosilicates have a SiP3 unit, that can be a planar triangle like carbonate CO3. The phosphorus atoms can be shared to form different patterns e.g. [Si2P6]10− which forms pairs, and [Si3P7]3− which contains two-dimensional double layer sheets. [SiP4]8− with isolated tetrahedra, and [SiP2]2− with a three dimensional network with shared tetrahedron corners. SiP clusters can be joined, not only by sharing a P atom, but also by way of a P-P bond. This does not happen with nitridosilicates or plain silicates.

Brigitte Eisenmann was a German chemist and a professor at the Technische Universität Darmstadt. She was the first woman professor for Chemistry at the Technische Universität Darmstadt. Together with Herbert Schäfer, she extended the definition of Zintl phases.

The selenide iodides are chemical compounds that contain both selenide ions (Se2−) and iodide ions (I−) and one or metal atoms. They are in the class of mixed anion compounds or chalcogenide halides.

The iodate fluorides are chemical compounds which contain both iodate and fluoride anions (IO3− and F−). In these compounds fluorine is not bound to iodine as it is in fluoroiodates.

The telluride iodides are chemical compounds that contain both telluride ions (Te2−) and iodide ions (I−). They are in the class of mixed anion compounds or chalcogenide halides.

A selenite fluoride is a chemical compound or salt that contains fluoride and selenite anions. These are mixed anion compounds. Some have third anions, including nitrate, molybdate, oxalate, selenate, silicate and tellurate.

The borosulfates are heteropoly anion compounds which have sulfate groups attached to boron atoms. Other possible terms are sulfatoborates or boron-sulfur oxides. The ratio of sulfate to borate reflects the degree of condensation. With [B(SO4)4]5- there is no condensation, each ion stands alone. In [B(SO4)3]3- the anions are linked into a chain, a chain of loops, or as [B2(SO4)6]6− in a cycle. Finally in [B(SO4)2]− the sulfate and borate tetrahedra are all linked into a two or three-dimensional network. These arrangements of oxygen around boron and sulfur can have forms resembling silicates. The first borosulfate to be discovered was K5[B(SO4)4] in 2012. Over 75 unique compounds are known.

The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds.

The nitridogermanates are chemical compounds containing germanium atoms bound to nitrogen. The simplest anion is GeN48−, but these are often condensed, with the elimination of nitrogen.

Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermannates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur. Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,

A Phosphide chloride is a mixed anion compound containing both phosphide (P3−) and chloride (Cl−) ions.

<span class="mw-page-title-main">Silanide</span> Anionic molecule derived from silane

A silanide is a chemical compound containing an anionic silicon(IV) centre, the parent ion being SiH−3. The hydrogen atoms can also be substituted to produced more complex derivative anions such as tris(trimethylsilyl)silanide (hypersilyl), tris(tert-butyl)silanide, tris(pentafluoroethyl)silanide, or triphenylsilanide. The simple silanide ion can also be called trihydridosilanide or silyl hydride.

Arsenidogermanates are chemical compounds that contain anions with arsenic bonded to germanium. They are in the category of tetrelarsenides, pnictidogermanates, or tetrelpnictides.

Arsenidostanates are chemical compounds that contain anions with arsenic bonded to tin. They are in the category of tetrelarsenides, pnictidostancates, or tetrelpnictides.

Sulfidogermanates or thiogermanates are chemical compounds containing anions with sulfur atoms bound to germanium. They are in the class of chalcogenidotetrelates. Related compounds include thiosilicates, thiostannates, selenidogermanates, telluridogermanates and selenidostannates.

Phosphide iodides or iodide phosphides are compounds containing anions composed of iodide (I−) and phosphide (P3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the phosphide chlorides, arsenide iodides antimonide iodides and phosphide bromides.

Phosphide bromides or bromide phosphides are compounds containing anions composed of bromide (Br−) and phosphide (P3−) anions. Usually phosphorus is covalently connected into more complex structures. They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the phosphide chlorides, phosphide iodides, nitride bromides, arsenide bromides, and antimonide bromides.

Arsenide bromides or bromide arsenides are compounds containing anions composed of bromide (Br−) and arsenide (As3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the arsenide chlorides, arsenide iodides, phosphide bromides, and antimonide bromides.

Arsenide iodides or iodide arsenides are compounds containing anions composed of iodide (I−) and arsenide (As3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the arsenide chlorides, arsenide bromides, phosphide iodides, and antimonide iodides.

References

  1. 1 2 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. 1 2 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. 1 2 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. 1 2 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. 1 2 3 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. 1 2 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. 1 2 3 4 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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