Abstract

<p>The influence of various polymeric matrices on the phosphorescence of organic molecules is illustrated for the case of 1, 2, 5, 6-dibenzanthracene. The phosphorescence spectra and decay times are compared with low-temperature glasses. Interaction of the aromatic hydrocarbon with the plastic matrices is shown to be greater than with the low-temperature glasses. This interaction is manifested by a higher quantum yield of phosphorescence (relative to fluorescence), but shorter decay times. The effect of the polymer on the triplet state is interpreted in terms of the vibrational structure of the phosphorescence spectra. The degree of polarization and decay time of the phosphorescence emission was studied in the range 77°-365°K and the results are related to the temperature dependence of rotation of the molecule in the matrix. The quenching action of oxygen on phosphorescence is demonstrated with film samples of 20-µ thickness.</p><p>The relevant physical properties of the plastics employed are discussed and details of sample preparation are presented.</p>

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  1. For a recent review of the organic triplet state, see S. K. Lower and M. A. El-Sayed, Chem. Rev. 66,199 (1966).
  2. G. Oster, N. Geacintov, and A. U. Khan, Nature 196, 1089 (1962).
  3. W. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
  4. E. V. Anufrieva and A. D. Saitzeva, Dokl, Akad. Nauk SSSR 24, 755 (1960); F. C. Unterleitner and E. I. Hormats, J. Phys. Chem. 69, 2516 (1965).
  5. G. Oster and Y. Nishijima, Fortschr. Hochpolymer. Forsch. 3, 313 (1964).
  6. G. Oster, J. Joussot-Dubien, and B. Broyde, J. Am. Chem. Soc. 81, 1869 (1959).
  7. G. Oster, N. Geacintov, and T. Cassen, Acta Physica Polon 26, 489 (1964).
  8. See, for example, C. C. Winding and G. D. Hiatt, Polymeric Materials (McGraw-Hill Book Co., New York, 1961).
  9. W. Sorenson and T. Campbell, Preparative Methods of Polymer Chemistry (Interscience Publishers, Inc., New York, 1961).
  10. T. Cassen, Doctoral dissertation, Polytechnic Institute of Brooklyn, 1966.
  11. L. M. Minsk, W. J. Priest, and W. O. Kenyon, J. Am. Chem. Soc. 63, 2715 (1941).
  12. E. Clar, Aromatische Kohlenwasserstoffe (Julius Springer-Verlag, Berlin, 1952), p. 198.
  13. M. A. El-Sayed, J. Opt. Soc. Am. 53, 797 (1963).
  14. T. Azumi and S. P. McGlynn, J. Chem. Phys. 37, 2413 (1962),
  15. F. Dörr, Angew. Chem. (English ed.) 5, 478 (1966).
  16. E. Clar and M. Zander, Chem. Ber. 89, 749 (1959).
  17. D. P. Craig and I. G. Ross, J. Chem. Soc. 1954, 1589 (1954).
  18. A. A. Ilyina and E. V. Shpol'ski, Dokl. Akad. Nauk SSSR 25, 585 (1951).
  19. H. Perkampus and L. Pohl, Z. Physik. Chem. (Frankfurt) 40, 314 (1962).
  20. The triplet-triplet spectra of DBA in plastics have been measured and are different from those in EPA.17
  21. P. Diken, A. Petrov, and B. Sveshnikov, Soviet Phys. JETP (English transl.) 21, 150 (1951).
  22. S. S. Stimler, J. Mol. Spectry. 16, 84 (1965).
  23. S. P. McGlynn, J. Daigre, and F. Smith, J. Chem. Phys. 39, 675 (1963).
  24. E. J. Bowen and B. Brocklehurst, J. Chem. Soc. 1955, 4320 (1955).
  25. E. V. Shpol'ski, Soviet Phys.-Usp. 77, 321 (1962); [English transl. 5, 522 (1962)].
  26. G. W. Robinson and R. P. Frosch, J. Chem. Phys. 37, 1962 (1962); 38, 1187 (1963).
  27. R. E. Kellogg and R. P. Schwenker, J. Chem. Phys. 41, 2860 (1964).
  28. S. G. Hadley, H. E. Rast, Jr., and R. A. Keller, J. Chem. Phys. 39, 705 (1963).
  29. N. K. Chaudhuri and M. A. El-Sayed, J. Chem. Phys. 43, 1423 (1965).
  30. G. W. Robinson, J. Chem. Phys. 46, 572 (1967).
  31. D. M. Grebenshchikov, V. A. Bultar, and V. V. Solodunov, Opt. i Spektroskopiya 21, 250 (1966).
  32. We are intlebted to Dr. A. Greenberg of New York University for this measurement.
  33. R. E. Kellogg and N. Convers-Wyeth, J. Chem. Phys. 45, 3156 (1966); W. Siebrand and D. F. Williams, J. Chem. Phys. 46, 403 (1967).
  34. E. C. Lim, J. D. Laposa, and J. M. H. Yu, J. Mopectryl. S. 19, 412 (1966).

Anufrieva, E. V.

E. V. Anufrieva and A. D. Saitzeva, Dokl, Akad. Nauk SSSR 24, 755 (1960); F. C. Unterleitner and E. I. Hormats, J. Phys. Chem. 69, 2516 (1965).

Azumi, T.

T. Azumi and S. P. McGlynn, J. Chem. Phys. 37, 2413 (1962),

Bowen, E. J.

E. J. Bowen and B. Brocklehurst, J. Chem. Soc. 1955, 4320 (1955).

Brocklehurst, B.

E. J. Bowen and B. Brocklehurst, J. Chem. Soc. 1955, 4320 (1955).

Broyde, B.

G. Oster, J. Joussot-Dubien, and B. Broyde, J. Am. Chem. Soc. 81, 1869 (1959).

Bultar, V. A.

D. M. Grebenshchikov, V. A. Bultar, and V. V. Solodunov, Opt. i Spektroskopiya 21, 250 (1966).

Campbell, T.

W. Sorenson and T. Campbell, Preparative Methods of Polymer Chemistry (Interscience Publishers, Inc., New York, 1961).

Cassen, T.

T. Cassen, Doctoral dissertation, Polytechnic Institute of Brooklyn, 1966.

G. Oster, N. Geacintov, and T. Cassen, Acta Physica Polon 26, 489 (1964).

Chaudhuri, N. K.

N. K. Chaudhuri and M. A. El-Sayed, J. Chem. Phys. 43, 1423 (1965).

Clar, E.

E. Clar, Aromatische Kohlenwasserstoffe (Julius Springer-Verlag, Berlin, 1952), p. 198.

E. Clar and M. Zander, Chem. Ber. 89, 749 (1959).

Convers-Wyeth, N.

R. E. Kellogg and N. Convers-Wyeth, J. Chem. Phys. 45, 3156 (1966); W. Siebrand and D. F. Williams, J. Chem. Phys. 46, 403 (1967).

Craig, D. P.

D. P. Craig and I. G. Ross, J. Chem. Soc. 1954, 1589 (1954).

Daigre, J.

S. P. McGlynn, J. Daigre, and F. Smith, J. Chem. Phys. 39, 675 (1963).

Diken, P.

P. Diken, A. Petrov, and B. Sveshnikov, Soviet Phys. JETP (English transl.) 21, 150 (1951).

Dörr, F.

F. Dörr, Angew. Chem. (English ed.) 5, 478 (1966).

El-Sayed, M. A.

N. K. Chaudhuri and M. A. El-Sayed, J. Chem. Phys. 43, 1423 (1965).

M. A. El-Sayed, J. Opt. Soc. Am. 53, 797 (1963).

For a recent review of the organic triplet state, see S. K. Lower and M. A. El-Sayed, Chem. Rev. 66,199 (1966).

Frosch, R. P.

G. W. Robinson and R. P. Frosch, J. Chem. Phys. 37, 1962 (1962); 38, 1187 (1963).

Geacintov, N.

G. Oster, N. Geacintov, and A. U. Khan, Nature 196, 1089 (1962).

G. Oster, N. Geacintov, and T. Cassen, Acta Physica Polon 26, 489 (1964).

Grebenshchikov, D. M.

D. M. Grebenshchikov, V. A. Bultar, and V. V. Solodunov, Opt. i Spektroskopiya 21, 250 (1966).

Greenberg, A.

We are intlebted to Dr. A. Greenberg of New York University for this measurement.

Hadley, S. G.

S. G. Hadley, H. E. Rast, Jr., and R. A. Keller, J. Chem. Phys. 39, 705 (1963).

Hardwick, R.

W. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).

Hiatt, G. D.

See, for example, C. C. Winding and G. D. Hiatt, Polymeric Materials (McGraw-Hill Book Co., New York, 1961).

Ilyina, A. A.

A. A. Ilyina and E. V. Shpol'ski, Dokl. Akad. Nauk SSSR 25, 585 (1951).

Joussot-Dubien, J.

G. Oster, J. Joussot-Dubien, and B. Broyde, J. Am. Chem. Soc. 81, 1869 (1959).

Keller, R. A.

S. G. Hadley, H. E. Rast, Jr., and R. A. Keller, J. Chem. Phys. 39, 705 (1963).

Kellogg, R. E.

R. E. Kellogg and N. Convers-Wyeth, J. Chem. Phys. 45, 3156 (1966); W. Siebrand and D. F. Williams, J. Chem. Phys. 46, 403 (1967).

R. E. Kellogg and R. P. Schwenker, J. Chem. Phys. 41, 2860 (1964).

Kenyon, W. O.

L. M. Minsk, W. J. Priest, and W. O. Kenyon, J. Am. Chem. Soc. 63, 2715 (1941).

Khan, A. U.

G. Oster, N. Geacintov, and A. U. Khan, Nature 196, 1089 (1962).

Laposa, J. D.

E. C. Lim, J. D. Laposa, and J. M. H. Yu, J. Mopectryl. S. 19, 412 (1966).

Lim, E. C.

E. C. Lim, J. D. Laposa, and J. M. H. Yu, J. Mopectryl. S. 19, 412 (1966).

Lower, S. K.

For a recent review of the organic triplet state, see S. K. Lower and M. A. El-Sayed, Chem. Rev. 66,199 (1966).

McGlynn, S. P.

T. Azumi and S. P. McGlynn, J. Chem. Phys. 37, 2413 (1962),

S. P. McGlynn, J. Daigre, and F. Smith, J. Chem. Phys. 39, 675 (1963).

Melhuish, W.

W. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).

Minsk, L. M.

L. M. Minsk, W. J. Priest, and W. O. Kenyon, J. Am. Chem. Soc. 63, 2715 (1941).

Nishijima, Y.

G. Oster and Y. Nishijima, Fortschr. Hochpolymer. Forsch. 3, 313 (1964).

Oster, G.

G. Oster, J. Joussot-Dubien, and B. Broyde, J. Am. Chem. Soc. 81, 1869 (1959).

G. Oster and Y. Nishijima, Fortschr. Hochpolymer. Forsch. 3, 313 (1964).

G. Oster, N. Geacintov, and T. Cassen, Acta Physica Polon 26, 489 (1964).

G. Oster, N. Geacintov, and A. U. Khan, Nature 196, 1089 (1962).

Perkampus, H.

H. Perkampus and L. Pohl, Z. Physik. Chem. (Frankfurt) 40, 314 (1962).

Petrov, A.

P. Diken, A. Petrov, and B. Sveshnikov, Soviet Phys. JETP (English transl.) 21, 150 (1951).

Pohl, L.

H. Perkampus and L. Pohl, Z. Physik. Chem. (Frankfurt) 40, 314 (1962).

Priest, W. J.

L. M. Minsk, W. J. Priest, and W. O. Kenyon, J. Am. Chem. Soc. 63, 2715 (1941).

Rast, Jr., H. E.

S. G. Hadley, H. E. Rast, Jr., and R. A. Keller, J. Chem. Phys. 39, 705 (1963).

Robinson, G. W.

G. W. Robinson, J. Chem. Phys. 46, 572 (1967).

G. W. Robinson and R. P. Frosch, J. Chem. Phys. 37, 1962 (1962); 38, 1187 (1963).

Ross, I. G.

D. P. Craig and I. G. Ross, J. Chem. Soc. 1954, 1589 (1954).

Saitzeva, A. D.

E. V. Anufrieva and A. D. Saitzeva, Dokl, Akad. Nauk SSSR 24, 755 (1960); F. C. Unterleitner and E. I. Hormats, J. Phys. Chem. 69, 2516 (1965).

Schwenker, R. P.

R. E. Kellogg and R. P. Schwenker, J. Chem. Phys. 41, 2860 (1964).

Shpol’ski, E. V.

E. V. Shpol'ski, Soviet Phys.-Usp. 77, 321 (1962); [English transl. 5, 522 (1962)].

A. A. Ilyina and E. V. Shpol'ski, Dokl. Akad. Nauk SSSR 25, 585 (1951).

Smith, F.

S. P. McGlynn, J. Daigre, and F. Smith, J. Chem. Phys. 39, 675 (1963).

Solodunov, V. V.

D. M. Grebenshchikov, V. A. Bultar, and V. V. Solodunov, Opt. i Spektroskopiya 21, 250 (1966).

Sorenson, W.

W. Sorenson and T. Campbell, Preparative Methods of Polymer Chemistry (Interscience Publishers, Inc., New York, 1961).

Stimler, S. S.

S. S. Stimler, J. Mol. Spectry. 16, 84 (1965).

Sveshnikov, B.

P. Diken, A. Petrov, and B. Sveshnikov, Soviet Phys. JETP (English transl.) 21, 150 (1951).

Winding, C. C.

See, for example, C. C. Winding and G. D. Hiatt, Polymeric Materials (McGraw-Hill Book Co., New York, 1961).

Yu, J. M. H.

E. C. Lim, J. D. Laposa, and J. M. H. Yu, J. Mopectryl. S. 19, 412 (1966).

Zander, M.

E. Clar and M. Zander, Chem. Ber. 89, 749 (1959).

Other (34)

For a recent review of the organic triplet state, see S. K. Lower and M. A. El-Sayed, Chem. Rev. 66,199 (1966).

G. Oster, N. Geacintov, and A. U. Khan, Nature 196, 1089 (1962).

W. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).

E. V. Anufrieva and A. D. Saitzeva, Dokl, Akad. Nauk SSSR 24, 755 (1960); F. C. Unterleitner and E. I. Hormats, J. Phys. Chem. 69, 2516 (1965).

G. Oster and Y. Nishijima, Fortschr. Hochpolymer. Forsch. 3, 313 (1964).

G. Oster, J. Joussot-Dubien, and B. Broyde, J. Am. Chem. Soc. 81, 1869 (1959).

G. Oster, N. Geacintov, and T. Cassen, Acta Physica Polon 26, 489 (1964).

See, for example, C. C. Winding and G. D. Hiatt, Polymeric Materials (McGraw-Hill Book Co., New York, 1961).

W. Sorenson and T. Campbell, Preparative Methods of Polymer Chemistry (Interscience Publishers, Inc., New York, 1961).

T. Cassen, Doctoral dissertation, Polytechnic Institute of Brooklyn, 1966.

L. M. Minsk, W. J. Priest, and W. O. Kenyon, J. Am. Chem. Soc. 63, 2715 (1941).

E. Clar, Aromatische Kohlenwasserstoffe (Julius Springer-Verlag, Berlin, 1952), p. 198.

M. A. El-Sayed, J. Opt. Soc. Am. 53, 797 (1963).

T. Azumi and S. P. McGlynn, J. Chem. Phys. 37, 2413 (1962),

F. Dörr, Angew. Chem. (English ed.) 5, 478 (1966).

E. Clar and M. Zander, Chem. Ber. 89, 749 (1959).

D. P. Craig and I. G. Ross, J. Chem. Soc. 1954, 1589 (1954).

A. A. Ilyina and E. V. Shpol'ski, Dokl. Akad. Nauk SSSR 25, 585 (1951).

H. Perkampus and L. Pohl, Z. Physik. Chem. (Frankfurt) 40, 314 (1962).

The triplet-triplet spectra of DBA in plastics have been measured and are different from those in EPA.17

P. Diken, A. Petrov, and B. Sveshnikov, Soviet Phys. JETP (English transl.) 21, 150 (1951).

S. S. Stimler, J. Mol. Spectry. 16, 84 (1965).

S. P. McGlynn, J. Daigre, and F. Smith, J. Chem. Phys. 39, 675 (1963).

E. J. Bowen and B. Brocklehurst, J. Chem. Soc. 1955, 4320 (1955).

E. V. Shpol'ski, Soviet Phys.-Usp. 77, 321 (1962); [English transl. 5, 522 (1962)].

G. W. Robinson and R. P. Frosch, J. Chem. Phys. 37, 1962 (1962); 38, 1187 (1963).

R. E. Kellogg and R. P. Schwenker, J. Chem. Phys. 41, 2860 (1964).

S. G. Hadley, H. E. Rast, Jr., and R. A. Keller, J. Chem. Phys. 39, 705 (1963).

N. K. Chaudhuri and M. A. El-Sayed, J. Chem. Phys. 43, 1423 (1965).

G. W. Robinson, J. Chem. Phys. 46, 572 (1967).

D. M. Grebenshchikov, V. A. Bultar, and V. V. Solodunov, Opt. i Spektroskopiya 21, 250 (1966).

We are intlebted to Dr. A. Greenberg of New York University for this measurement.

R. E. Kellogg and N. Convers-Wyeth, J. Chem. Phys. 45, 3156 (1966); W. Siebrand and D. F. Williams, J. Chem. Phys. 46, 403 (1967).

E. C. Lim, J. D. Laposa, and J. M. H. Yu, J. Mopectryl. S. 19, 412 (1966).

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