Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

EPR Study of${\gamma}(1,2)-[H{_n}SiV^{IV}VW_{10}O_{40}]^{(7-n)-}$ (n = 0, 1 or 2). Identification of Four One-Electron Reduction Products and Evidence for Proton Transfer in the Solid State

  • Jeongmin Park (Department of Chemistry, Sogang University) ;
  • Hyunsoo So (Department of Chemistry, Sogang University)
  • Published : 1994.09.20
Download PDF
⟨ Previous Next ⟩

Abstract

Several one-electron reduction products of ${\gamma}$(1,2)-[$H_nSiV_2W_{10}O_{40}]^{(6-n)-}$ were separated by precipitating or coprecipitating with diamagnetic host compounds at different pH. Mono-and diprotonated species, 1 and 2, in powder samples exhibit aPR spectra characteristic of a mononuclear oxovanadium species, indicating that the unpaired electron is trapped at one vanadium atom. The EPR spectrum of the unprotonated species 0 shows 15 parallel lines, indicating that the unpaired electron interacts equally with two vanadium atoms. While different species were precipitated depending upon the pH of the solution and the charge of the host anion, only one species 1' was formed in the frozen solutions at pH 3.2-4.7. The EPR spectrum of 1' indicates that the unpaired electron is trapped at one vanadium atom and 1/16 of the spin density is delocalized onto the second vanadium atom. The species 1' is probably another form of the monoprotonated species. The EPR spectra show that some of 2 transform into 1 and some of 0 transform into 1' in the solid state at low temperatures. It is suggested that proton transfer between the heteropolyanion and water molecues in the solid state is involved in these transformations.

Keywords

References

  1. J. Am. Chem. Soc. v.102 Mossoba, M. M.;O'Connor, C. J.;Pope, M. T.;Sinn, E.;Herve, G.;Teze, A.
  2. J. Am. Chem. Soc. v.105 Harmalker, S. P.; Leparulo, M. A.;Pope, M. T.
  3. Bull. Korean Chem. Soc. v.7 Lee, C. W.;So. H.
  4. Bull. Korean Chem. Soc. v.7 Lee, C. W.;So. H.;Lee, K. R.
  5. Bull. Korean Chem. Soc. v.8 So, H.;Lee, C. W.;Lee, D.
  6. Bull. Korean Chem. Soc. v.7 Lee, C. W.;So. H.
  7. Bull. Korean Chem. Soc. v.11 So, H.;Lee, C. W.
  8. Inorg. Chem. v.30 Canny, J.;Thouvenot, R.;Teze, A.;Herve, G.;Leparulo-Loftus, M.;Pope, M. T.
  9. J. Am. Chem. Soc. v.108 Domaille P. J.;Harlow, R. L.
  10. Bull. Korean Chem. Soc. v.9 Lee, C. W.;So, H.;Lee, K. R.
  11. Proc. Roy. Soc. v.A214 Bleaney, B.;Bowers, K. D.
  12. J. Inorg. Nucl. Chem. v.36 So, H.;Flynn, Jr., C. M.;Pope, M. T.
  13. Inorg. Chem. v.12 Smith, D. P.;So, H.;Bender, J.;Pope, M. T.
  14. J. Magn. Resonance v.35 Nilges, M. J.;Belford, R. L.
  15. Inorg. Chem. v.25 Knoth, W. H.;Domaille, P. J.;Harlow, R. L.
  16. Organometalics v.4 Knoth, W. H.;Domaille, P. J.;Farlee, R. D.
  17. Inorg. Chem. v.26 Finke, R. G.;Droege, M. W.;Domaille, P. J.
  18. J. Am. Chem. Soc. v.109 Day, V. W.;Klemperer, W. G.;Maltbie, D. J.
  19. Inorg. Chem. v.10 Flynn, Jr., C. M.; Pope, M. T.
  20. J. Am. Chem. Soc v.108 Finke, R. G.;Rapko, B.;Saxton, R. J.;Domaille, P. J.
  21. Science v.228 Day, V. W.;Klemperer, W. G.
  22. J. Am. Chem. Soc v.114 Chen, Q.;Goshorn, D. P.;Scholes, C. P.;Tan, X.;Zubieta, J.
  23. Naturforschg. v.24b Lange, G.;Hahn, H.;Dehnicke, K. Z.
  24. Inorg. Chem. v.22 Rocchiccioli-Deltcheff, C.;Fournier, M.;Franck, R.;Thouvenot, R.

Cited by

  1. Coexistence of one-electron- and monoprotonated two-electron-reduced species of the K5[PMo2VW9O40] · 24H2O heteropolyoxometalate identified by EPR vol.20, pp.3, 1994, https://doi.org/10.1007/bf03162286
  2. Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions vol.24, pp.17, 1994, https://doi.org/10.1002/chem.201705711