Citation: Ai-Ling Li, Yan-Ping Ma, Dong Qiu. Formation of six-coordinated silicon in calcium phosphosilicate xerogels assisted by polyols at low temperature and pressure[J]. Chinese Chemical Letters, ;2015, 26(6): 768-772. doi: 10.1016/j.cclet.2015.03.004 shu

Formation of six-coordinated silicon in calcium phosphosilicate xerogels assisted by polyols at low temperature and pressure

1.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Ai-Ling Li, Dong Qiu,
Received Date: 3 November 2014
Available Online: 9 February 2015
Fund Project: This work was supported by the State Key Development Program of Basic Research of China (No. 2012CB933200) (No. 2012CB933200)National Natural Science Foundation of China (No. 51173193). (No. 51173193)

Silicon is usually found to be four-coordinated when neighbored with oxygen. Six-coordinated silicon is only seen in samples at very specific composition or made at high temperature/pressure. In this study, we managed to synthesize calciumphosphosilicate xerogels containing six-coordinated silicon with the help of polyols by sol-gel method, without the need of treatment at high temperature or high pressure. Both phosphorus precursors and polyols were found to be essential for the formation of six-coordinated silicon species; in the absence of either species, only normal four-coordinated silicon was observed under otherwise identical conditions. Samples containing six-coordinated silicon sites were found to release silicon species faster than those without six-coordinated silicon sites upon dissolved in water, suggesting that six-coordinated silicon species have higher reactivity toward hydrolysis.
- Phosphosilicate,
- Six-coordinated silicon,
- Polyols,
- MAS-NMR
1. [1]
  [1] M. Nogami, K. Miyamura, Y. Abe, Fast protonic conductors of water-containing P₂O₅–ZrO₂–SiO₂ glasses, J. Electrochem. Soc. 144 (1997) 2175–2178.
2. [2]
  [2] N.J. Clayden, S. Esposito, P. Pernice, A. Aronne, Solid state ¹H NMR study, humidity sensitivity and protonic conduction of gel derived phosphosilicate glasses, J. Mater. Chem. 12 (2002) 3746–3753.
3. [3]
  [3] E.A. Abou Neel, D.M. Pickup, S.P. Valappil, R.J. Newport, J.C. Knowles, Bioactive functional materials: a perspective on phosphate-based glasses, J. Mater. Chem. 19 (2009) 690–701.
4. [4]
  [4] L.L. Hench, Bioceramics: from concept to clinic, J. Am. Ceram. Soc. 74 (1991) 1487– 1510.
5. [5]
  [5] J. Ide, K. Ozutsumi, H. Kageyama, XAFS study of six-coordinated silicon in R₂O–SiO₂–P₂O₅ (R = Li, Na, K) glasses, J. Non-Cryst. Solids 353 (2007) 1966–1969.
6. [6]
  [6] P. Melnikov, S.B. Santagnelli, F.J. dos Santos, et al., Phosphate functionalization of spongiolite surface, Mater. Chem. Phys. 82 (2003) 980–983.
7. [7]
  [7] R. Dupree, D. Holland, M.G. Mortuza, J.A. Collins, M.W.G. Lockyer, Magic angle spinning NMR of alkali phosphor-alumino-silicate glasses, J. Non-Cryst. Solids 112 (1989) 111–119.
8. [8]
  [8] N.J. Clayden, S. Esposito, P. Pernice, A.J. Aronne, Solid state 29Si and ³¹P NMR study of gel derived phosphosilicate glasses, J. Mater. Chem. 11 (2001) 936–943.
9. [9]
  [9] I. EI-Sayed, Y. Hatanaka, S. Onozawa, M.J. Tanaka, Unusual locking of silicon chains in to all-transoid conformation by pentacoordinate silicon atoms, Am. Chem. Soc. 123 (2001) 3597–3598.
10. [10]
  [10] I. El-Sayed, Y. Hatanaka, C. Muguruma, et al., Synthesis, X-ray structure, and electronic properties of oligosilanes containing pentacoordinate silicon moieties at internal positions, J. Am. Chem. Soc. 121 (1999) 5095–5096.
11. [11]
  [11] C. Muguruma, N. Koga, Y. Hatanaka, et al., Theoretical study of ultraviolet absorption spectra of tetra- and pentacoordinate silicon compounds, J. Phys. Chem. A 104 (2000) 4928–4935.
12. [12]
  [12] I. Kalikhman, O. Girshberg, L. Lameyer, D. Stalke, D. Kost, Tautomeric equilibrium between penta- and hexacoordinate silicon chelates. A chloride bridge between two pentacoordinate silicons, J. Am. Chem. Soc. 123 (2001) 4709–4716.
13. [13]
  [13] M. Nakash, M. Goldvaser, Formation of hypervalent complexes of PhCCSiF₃ with pyridine through intermolecular silicon nitrogen interaction, J. Am. Chem. Soc. 126 (2004) 3436–3437.
14. [14]
  [14] I. Kalikhman, B. Gostevskii, O. Girshberg, S. Krivonos, D. Kost, Donor-stabilized silyl cations 4: N-isopropylidene hydrazides, novel bidentate ligands for pentaand hexacoordinate silicon chelates, Organometallics 21 (2002) 2551–2554.
15. [15]
  [15] N. Kano, F. Komatsu, M. Yamamura, T. Kawashima, Reversible photoswitching of the coordination numbers of silicon in organosilicon compounds bearing a 2-(phenylazo) phenyl group, J. Am. Chem. Soc. 128 (2006) 7097–7109.
16. [16]
  [16] J.B. Lambert, S.R. Singer, Self-assembled macrocycles with pentavalent silicon linkages, J. Organomet. Chem. 689 (2004) 2293–2302.
17. [17]
  [17] G. Serghiou, R. Boehler, A. Chopelas, Reversible coordination changes in crystalline silicates at high pressure and ambient temperature, J. Phys. Condens. Matter 12 (2000) 849–857.
18. [18]
  [18] M. Nogami, K. Miyamura, Y. Kawasaki, Y. Abe, Six-coordinated silicon in SrO– P2O5–SiO2 glasses, J. Non-Cryst. Solids 211 (1997) 208–213.
19. [19]
  [19] T.L. Weeding, B.H.W.S.W. de Jong, S. Veeman, B.G. Aitken, Silicon coordination changes from 4-fold to 6-fold on devitrification of silicon phosphate glass, Nature 318 (1985) 352–353.
20. [20]
  [20] E. Ohtani, F. Taulelle, C.A. Angell, Al3+ coordination changes in liquid aluminosilicates under pressure, Nature 314 (1985) 78–81.
21. [21]
  [21] X. Xue, J.F. Stebbins, M. Kanzaki, R.G. Tronnes, Silicon coordination and speciation changes in a silicate liquid at high pressures, Science 245 (1989) 962–964.
22. [22]
  [22] J.F. Stebbins, M. Kanzaki, Local structure and chemical shifts for six-coordinated silicon in high-pressure mantle phases, Science 251 (1991) 294–298.
23. [23]
  [23] S.D. Kinrade, J.W.D. Nin, A.S. Schach, et al., Stable five- and six-coordinated silicate anions in aqueous solution, Science 285 (1999) 1542–1545.
24. [24]
  [24] P. Hartmann, C. Jana, J. Vogel, C. Jager, P-31 MAS and 2D exchange NMR of crystalline silicon phosphates, Chem. Phys. Lett. 258 (1996) 107–112.
25. [25]
  [25] D. Miyabe, M. Takahashi, Y. Tokuda, T. Yoko, T. Uchino, Structure and formation mechanism of six-fold coordinated silicon in phosphosilicate glasses, Phys. Rev. B 71 (2005) 172202.
26. [26]
  [26] C. Coelho, F. Babonneau, T. Azaís, et al., Chemical bonding in silicophosphate gels: contribution of dipolar and J-derived solid state NMR techniques, J. Sol–Gel. Sci. Technol. 40 (2006) 181–189.
27. [27]
  [27] S.P. Szu, L.C. Klein, M. Greenblatt, Effect of precursors on the structure of phosphosilicate gels-Si-29 and P-31 MAS NMR-study, J. Non-Cryst. Solids 143 (1992) 21–30.
28. [28]
  [28] A. Li, D. Wang, J. Xiang, et al., Insights into new calcium phosphosilicate xerogels using an advanced characterization methodology, J. Non-Cryst. Solids 357 (2011) 3548–3555.
29. [29]
  [29] R. Dupree, D. Holland, M.G. Mortuza, 6-Coordinated silicon in glasses, Nature 328 (1987) 416–417.
30. [30]
  [30] S. Prabakar, K.J. Rao, C.N.R. Rao, A MAS NMR investigation of lead phosphosilicate glasses: the nature of the highly deshielded six-coordinated silicon, Mater. Res. Bull. 26 (1991) 285–294.
31. [31]
  [31] M.G. Mortuza, M.R. Ahsan, J.A. Chudek, G. Hunter, First evidence for the coexistence of four-, five- and six-coordinated silicon in glasses prepared at ambient pressure, Chem. Commun. (2000) 2055–2056.
32. [32]
  [32] V. Salih, K. Franks, M. James, G.W. Hastings, J.C. Knowles, Development of soluble glasses for biomedical use: Part II. The biological response of human osteoblast cell lines to phosphate-based soluble glasses, J. Mater. Sci.: Mater. Med. 11 (2000) 615-620.
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