Polythiazyl

Polythiazyl (polymeric sulfur nitride), (SN)x, is an electrically conductive, gold- or bronze-colored polymer with metallic luster. It was the first conductive inorganic polymer discovered[1][2] and was also found to be a superconductor at very low temperatures (below 0.26 K).[3][4] It is a fibrous solid, described as "lustrous golden on the faces and dark blue-black", depending on the orientation of the sample. It is air stable and insoluble in all solvents.[5]

Polythiazyl
Names
Other names
polythiazyl
poly(sulfur nitride)
Identifiers
ChemSpider
  • none
Properties
(SN)x
Appearance bronze colour, metallic lustre[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

History

The compound was first reported as early as 1910 by F.P. Burt, who obtained it by heating tetrasulfur tetranitride in vacuum over silver wool.[6]

The compound was the first non-metallic compound in which superconductivity could be demonstrated. However, the relatively low transition temperature at about 0.3 K makes a practical application unlikely.[7][8]

Properties

Polythiazyl is a metallic-golden and shiny, crystalline but fibrous material.[8] The polymer is mostly inert to oxygen and water, but decomposes in air to a grey powder.[9][10] At temperatures above 240 °C explosive decomposition can occur.[11] The compound also explodes on impact.[10]

Polythiazyl shows an anisotropic electrical conductivity. Along the fibres or SN chains, the bond is electrically conductive, perpendicular to it acts as an insulator. The one-dimensional conductivity is based on the bonding conditions in the S-N chain, where each sulfur atom provides two π electrons and each nitrogen atom provides one π electron to form two-center 3π electron bonding units.[8]

Two polymorphic crystal forms were observed in the compound. The monoclinic form I obtained from the synthesis can be converted into an orthorhombic form II by mechanical treatment such as grinding.[12]

Structure and bonding

The material is a polymer. The S and N atoms on adjacent chains align.[2][13][14] Several resonance structures can be written.[15]

The structure of the crystalline compound was resolved by X-ray diffraction. This showed alternating SN bond lengths of 159 pm and 163 pm and SNS bond angles of 120 °C and NSN bond angles of 106 °C.[16][17][9][8]

Synthesis

Polythiazyl is synthesized by the polymerization of the dimer disulfur dinitride (S2N2), which is in turn synthesized from the cyclic alternating tetramer tetrasulfur tetranitride (S4N4).[2] Conversion from cyclic tetramer to dimer is catalysed with hot silver wool.[2][1][18]

S4N4 + 8 Ag → 4 Ag2S + 2 N2
S4N4 (w/ Ag2S catalyst) → 2 S2N2 (w/ 77K cold finger) → S2N2
S2N2 (@ 0°C, sublimes to surface) → thermal polymerization → (SN)x

Uses

Due to its electrical conductivity, polythiazyl is used in LEDs, transistors, battery cathodes, and solar cells.[18]

Literature

King, R.S.P.: Novel chemistry and applications of polythiazyl, Doctoral Thesis Loughborough University 2009, pdf-Download

References
  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 725–727. ISBN 978-0-08-037941-8.
  2. Goehring, Margot; Voigt, Dietrich (1953). "Über die Schwefelnitride (SN)2 und (SN)x". Die Naturwissenschaften (in German). 40 (18): 482. doi:10.1007/BF00628990. ISSN 0028-1042.
  3. Labes, M. M.; Love, P.; Nichols, L. F. (1979). "Polysulfur Nitride - a Metallic, Superconducting Polymer". Chemical Reviews. 79 (1): 1–15. doi:10.1021/cr60317a002.
  4. Harry R. Allcock (20 September 2011). Introduction to Materials Chemistry. John Wiley & Sons. p. 131. ISBN 978-1-118-21098-7. Retrieved 29 June 2012.
  5. A. G. MacDiarmid; C. M. Mikulsk; A. J. Heeger; A. F. Garito (1983). "Polymeric Sulfur Nitride (Polythiazyl), (SN)x". Inorganic Syntheses. 22: 143. doi:10.1002/9780470132531.ch31.
  6. Burt, Frank Playfair (1910). "XCIX.—A new sulphide of nitrogen" (PDF). J. Chem. Soc., Trans. 97: 1171–1174. doi:10.1039/CT9109701171. ISSN 0368-1645.
  7. Labes, M.M.; Love, P.; Nichols, L.F.: Polysulfur nitride - a metallic, superconducting polymer in Chem. Rev. 79 (1979) 1–15, doi:10.1021/cr60317a002.
  8. Alsfasser, R.; Janiak, C.; Klapötke, T.M.; Meyer, H.-J.: Moderne Anorganische Chemie, Herausgeber Riedel, E., 3. Auflage 2007, Walter de Gruyter GmbH & Co. KG, Berlin/Boston, ISBN 978-3-11-019060-1, S. 129–132, (abgerufen über De Gruyter Online).
  9. MacDiarmid, A.G.; Mikulski, C.M.; Saran, M.S.; Russo, P.J.; Cohen, M.J.; Bright, A.A.; Garito, A.F.; Heeger, A.J.: Synthesis and Selected Properties of Polymeric Sulfur Nitride, (Polythiazyl), (SN)x in Advances in Chemistry 150 (2009) 63–72, doi:10.1021/ba-1976-0150.ch006.
  10. Entry on Schwefel-Stickstoff-Verbindungen. at: Römpp Online. Georg Thieme Verlag, retrieved 2. März 2017.
  11. Wiberg, E.; Wiberg, N.; Holleman, A.F.: Anorganische Chemie, 103. Auflage, 2017 Walter de Gruyter GmbH & Co. KG, Berlin/Boston, ISBN 978-3-11-026932-1, S. 681, (abgerufen über De Gruyter Online).
  12. Baughman, R.H.; Apgar, P.A.; Chance, R.R.; MacDiarmid, A.G.; Garito, A.F.: A New Phase of (SN)x in J. Chem. Soc. Chem. Comm. 1977, 49–50, doi:10.1039/C39770000049.
  13. Goehring, Margot (1956). "Sulphur nitride and its derivatives". Quarterly Reviews, Chemical Society. 10 (4): 437. doi:10.1039/qr9561000437. ISSN 0009-2681.
  14. Cohen, M.J .; Garito, A. F.; Heeger, A. J.; MacDiarmid, A. G.; Mikulski, C. M.; Saran, M. S.; Kleppinger, J. (1976). "Solid state polymerization of S2N2 to (SN)x". Journal of the American Chemical Society. 98: 3844–3848. doi:10.1021/ja00429a018.
  15. Okada, M.; Tanaka, K.; Takata, A.; Yamabe, T. (1993). "Examination of Electronic Phase of the Hartree-Fock Solution of an Isolated Polythiazyl Chain". Synthetic Metals. 59 (2): 223–230. doi:10.1016/0379-6779(93)91029-2.
  16. Boudeulle, M.: in Cryst. Struct. Comm. 4 (1975) 9–13.
  17. MacDiarmid, A.G.; Mikulski, C.M.; Russo, P.J.; Saran, M.S.; Garito, A.F.; Heeger, A.J.: Synthesis and structure of the polymeric metal, (SN)x, and its precursor, S2N2 in J. Chem. Soc. Chem. Comm. 1975, 476–477, doi:10.1039/C39750000476.
  18. Ronald D. Archer (26 February 2001). Inorganic and Organometallic Polymers. John Wiley & Sons. p. 213. ISBN 978-0-471-24187-4. Retrieved 29 June 2012.
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