Preparation of a novel CdS nanocluster material from a thiophenolate-capped CdS cluster by chemical removal of SPh^- ligands

Abstract

Oxidation of the surface-capping SPh^- ligands of the CdS cluster [S₄Cd₁₀(SPh)₁₆ ]^4- in solution has been explored as a route to the synthesis of larger, well defined nanocrystals of CdS. Iodine was found to oxidise and remove the SPh^- ligands and effect the growth of a CdS cluster with a sharp UV–VIS absorption peak at 371 nm. Electrospray mass spectra indicate that the first step in the transformation involves the loss of the four [Cd(SPh)₄ ] units at the cluster corners. Characterisation by FTIR and UV–VIS spectroscopy and X-ray powder diffraction showed that the material consists of iodide-capped clusters of approximately 15 Å diameter. The isolated material redissolved in DMF where its emission spectrum showed a strong broad band at 510 nm.

References

1. M. L. Steigerwald and L. E. Brus, Acc. Chem. Res., 1990, 23, 183; Y. Wang, N. Herron, W. Mahler and A. Suna, J. Opt. Soc. Am. B: Opt. Phys., 1989, 6, 808; H. Weller, Angew. Chem., Int. Ed. Engl., 1993, 32, 41; A. Henglein, Chem. Rev., 1989, 89, 1861; Y. Wang and N. Herron, J. Phys. Chem., 1991, 95, 525.
2. A. P. Alivisatos, Science, 1996, 271, 933; H. Weller, Angew. Chem., Int. Ed. Engl., 1996, 35, 1079.
3. C. B. Murray, D. J. Norris and M. G. Bawendi, J. Am. Chem. Soc., 1993, 115, 8706.
4. N. Herron, Y. Wang and H. Eckert, J. Am. Chem. Soc., 1990, 112, 1322.
5. Y. Nosaka, H. Shigeno and T. Ikeuchi, J. Phys. Chem., 1995, 99, 8317.
6. Y. Nosaka, K. Yamaguchi, H. Miyama and H. Hayashi, Chem. Lett., 1988, 605.
7. D. Hayes, O. I. Micic, M. T. Nenadovic, V. Swayambunathan and D. Meisel, J. Phys. Chem., 1989, 93, 4603.
8. N. Herron, A. Suna and Y. Wang, J. Chem. Soc., Dalton Trans., 1992, 2329.
9. N. Herron, J. C. Calabrese, W. E. Farneth and Y. Wang, Science, 1993, 259, 1426.
10. T. Vossmeyer, G. Reck, B. Schulz, L. Katsikas and H. Weller, J. Am. Chem. Soc., 1995, 117, 12881.
11. T. Vossmeyer, L. Katsikas, M. Giersig, I. G. Popovic, K. Diesner, A. Chemseddine, A. Eychmüller and H. Weller, J. Phys. Chem., 1994, 98, 7665.
12. I. G. Dance, A. Choy and M. L. Scudder, J. Am. Chem. Soc., 1984, 106, 6285.
13. P. A. W. Dean, J. J. Vittal and N. C. Payne, Inorg. Chem., 1987, 26, 1683.
14. L. J. Arnold, J. Chem. Educ., 1992, 69, 811.
15. I. G. Dance and K. J. Fisher, Prog. Inorg. Chem., 1994, 41, 637.
16. Y. Wang and N. Herron, Phys. Rev. B, 1990, 42, 7253.
17. T. Türk, U. Resh, M. A. Fox and A. Vogler, J. Phys. Chem., 1992, 96, 3818.
18. T. Løver, G. A. Bowmaker, J. M. Seakins and R. P. Cooney, Chem. Mater., in press.
19. T. Løver, G. A. Bowmaker, W. Henderson and R. P. Cooney, Chem. Commun., 1996, 683.
20. T. Løver, W. Henderson, G. A. Bowmaker, J. M. Seakins and R. P. Cooney, Inorg. Chem., submitted.
21. P. L. Goggin, R. J. Goodfellow and K. Kessler, J. Chem. Soc., Dalton Trans., 1977, 1914.