Abstract
Radical cations are generated via monophotonic processes upon irradiation of poly(methylphenyl silylene) (PMPSi), poly(biphenylmethyl silylene) (PBMSi), poly(dihexyl silylene) (PDHeSi), and poly(hexylmethyl silylene) (PHeMSi) in dilute tetrahydrofuran solution with 15- or 20-ns flashes of 266- or 347-nm light, respectively. This was inferred from electrical conductivity measurements. Typical quantum yields Φ(ion) are as follows: for PBMSi, 4×102 (λinc=266nm) and 3×103 (λinc=347nm); and for PDHeSi, 8×103 (λinc=266nm) and 9×104 (λinc=347nm). In all cases, a significant portion of the transient absorption spectrum recorded at the end of the flash is attributed to the spectrum of the radical cation. The latter strongly overlaps the spectra of other intermediates (presumably silyl radical and silylene).
Similar content being viewed by others
References
A. Eckhardt, S. Nespurek, and W. Schnabel,Ber. Bunsenges. Phys. Chem. 98, 1325 (1994).
Y. Ohsako, J. R. G. Thorne, C. M. Phillips, J. M. Zeigler, and R. M. Hochstrasser,J. Phys. Chem. 93, 4408 (1989).
R. V. Todesco and P. V. Kamat,Macromolecules 19, 196 (1986).
T. Karatsu, R. D. Miller, R. Sooriyakumaran, and J. Michl,J. Am. Chem. Soc. 11, 1140 (1989).
A. Watanabe and M. Matsuda,Macromolecules 25, 484 (1992).
C. Chatgilialoglu, K. U. Ingold, K. Lusztyk, A. S. Nazran, and J. C. Scaiano,Organometallics 2, 1332 (1983).
I. Kminek, S. Nespurek, E. Brynda, J. Pfleger, V. Cimrova, and W. Schnabel,Collect. Czech. Chem. Commun. 58, 2337 (1993).
F. Brynda, S. Nespurek, and W. Schnabel,Chem. Phys. 175, 459 (1993).
V. Cimrova, I. Kminek, S. Nespurek, and W. Schnabel,Synth. Met. 64, 271 (1994).
A. Eckhardt, N. Yars, T. Wollny, S. Nespurek, and W. Schnabel,Ber. Bunsenges. Phys. Chem. 98, 853 (1994).
A. Eckhardt, V. Herden, S. Nespurek, and W. Schnabel,Phil. Mag. B 71, 239 (1995).
H. Valerian, F. Brynda, S. Nespurek, and W. Schnabel,J. Appl. Phys. 78, 6071 (1995).
K. A. Klingensmith, J. W. Downing, R. F. Miller, and J. Michl,J. Am. Chem. Soc. 108, 7438 (1986).
M. Fujino,Chem. Phys. Lett. 136, 451 (1986).
M. Stolka, H. J. Yuh, K. M. McGrane, and D. M. Pai,J. Polym. Sci. Polym. Lett. 25, 823 (1987).
M. A. Abkowitz, M. Stolka, R. J. Weagley, K. M. McGrane, and F. E. Knier,Adv. Chem. Ser. 224, 467 (1990).
A. Fekhardt, doctoral thesis (Technical University Berlin, 1995).
R. Kuhlmann and W. Schnabel,J. Photochem. 7, 287 (1977).
S. Irie, K. Oka, and M. Irie,Macromolecules 21, 110 (1988).
H. Ban, K. Sukegawa, and S. Tagawa,Macromolecules 20, 1775 (1987).
S. Tagawa,Polym. Preprints 31, 242 (1990).
N. R. Kestner, inRadiation Chemistry, Farhatazis and M. A. Rodgers, eds. (VHC, Weinheim, 1987), Chap. 8.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Eckhardt, A., Schnabel, W. Laser flash photolysis of poly(silylenes) in dilute solution. Generation of ionic species. J Inorg Organomet Polym 6, 95–110 (1996). https://doi.org/10.1007/BF01098321
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF01098321