Abstract

In the method of photoselection for measuring molecular polarization, it is not necessary that the molecule be embedded in a crystal of known structure, but merely rigidly fixed in a random arrangement. In this paper the possibility of using a plastic as the host solvent is examined. This would replace the previously used mixtures of organic solvents that form glasses at 77°K, and which, because of experimental conditions, might give rise to great depolarization effects. In methyl methacrylate polymer (Lucite), the phosphorescence of phenanthrene, coronene, and pyrazine is found to be polarized at room and liquid-nitrogen temperatures. The measured degree of polarization in the plastic is found to be in good agreement with the expected value. The effect on the degree of polarization of temperature, concentration, thickness, and shape of the plastic sample is discussed. The importance of using this method for further polarization investigations to increase our understanding of the structure and spectroscopic properties of complex luminescent guest molecules, as well as the internal structure and motions of different host polymers, is pointed out.

© 1963 Optical Society of America

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References

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  1. D. S. McClure, J. Chem. Phys. 22, 1668 (1954).
    [Crossref]
  2. T. Förster, Fluoreszenz Organischer Verbindungen (Vandenhoech und Ruprecht, Göttingen, Germany, 1951).
  3. P. P. Feofilov, The Physical Bases of Polarized Emission (Consultants Bureau, New York, 1961).
  4. A. Albrecht, J. Mol. Spectry. 6, 84 (1961).
    [Crossref]
  5. W. H. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
    [Crossref]
  6. R. S. Moore and M. W. Windsor, “Molecular Spectra and Molecular Structure,” Meeting, Columbus, Ohio, 1962.
  7. P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949).
  8. V. Krishna and L. Goodman, J. Chem. Phys. 36, 2217 (1962).
    [Crossref]
  9. M. A. El-Sayed and R. G. Brewer, “Polarization of the π*→ π and π*→ n Phosphorescence Spectrum of Nitrogen Heterocyclics,” J. Chem. Phys. (to be published).
  10. M. A. El-Sayed, Nature 197, 481 (1963).
    [Crossref]
  11. V. Krishna and L. Goodman, J. Chem. Phys. 37, 912 (1962).
    [Crossref]
  12. M. A. El-Sayed, Nature 197, 481 (1963).
    [Crossref]
  13. D. S. McClure, J. Chem. Phys. 19, 670 (1951).
    [Crossref]
  14. D. P. Craig and I. Ross, J. Chem. Soc. 1954, 1589.
  15. M. A. El-Sayed and T. Pavlopoulos, “Polarization of the Triplet–Triplet Absorption Spectrum of Some Polyacenes,” J. Chem. Phys. (to be published).
  16. A. Albrecht, J. Chem. Phys. 33, 156 (1960).
    [Crossref]

1963 (2)

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

1962 (3)

V. Krishna and L. Goodman, J. Chem. Phys. 37, 912 (1962).
[Crossref]

W. H. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
[Crossref]

V. Krishna and L. Goodman, J. Chem. Phys. 36, 2217 (1962).
[Crossref]

1961 (1)

A. Albrecht, J. Mol. Spectry. 6, 84 (1961).
[Crossref]

1960 (1)

A. Albrecht, J. Chem. Phys. 33, 156 (1960).
[Crossref]

1954 (1)

D. S. McClure, J. Chem. Phys. 22, 1668 (1954).
[Crossref]

1951 (1)

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

Albrecht, A.

A. Albrecht, J. Mol. Spectry. 6, 84 (1961).
[Crossref]

A. Albrecht, J. Chem. Phys. 33, 156 (1960).
[Crossref]

Brewer, R. G.

M. A. El-Sayed and R. G. Brewer, “Polarization of the π*→ π and π*→ n Phosphorescence Spectrum of Nitrogen Heterocyclics,” J. Chem. Phys. (to be published).

Craig, D. P.

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

El-Sayed, M. A.

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

M. A. El-Sayed and R. G. Brewer, “Polarization of the π*→ π and π*→ n Phosphorescence Spectrum of Nitrogen Heterocyclics,” J. Chem. Phys. (to be published).

M. A. El-Sayed and T. Pavlopoulos, “Polarization of the Triplet–Triplet Absorption Spectrum of Some Polyacenes,” J. Chem. Phys. (to be published).

Feofilov, P. P.

P. P. Feofilov, The Physical Bases of Polarized Emission (Consultants Bureau, New York, 1961).

Förster, T.

T. Förster, Fluoreszenz Organischer Verbindungen (Vandenhoech und Ruprecht, Göttingen, Germany, 1951).

Goodman, L.

V. Krishna and L. Goodman, J. Chem. Phys. 37, 912 (1962).
[Crossref]

V. Krishna and L. Goodman, J. Chem. Phys. 36, 2217 (1962).
[Crossref]

Hardwick, R.

W. H. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
[Crossref]

Krishna, V.

V. Krishna and L. Goodman, J. Chem. Phys. 36, 2217 (1962).
[Crossref]

V. Krishna and L. Goodman, J. Chem. Phys. 37, 912 (1962).
[Crossref]

McClure, D. S.

D. S. McClure, J. Chem. Phys. 22, 1668 (1954).
[Crossref]

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

Melhuish, W. H.

W. H. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
[Crossref]

Moore, R. S.

R. S. Moore and M. W. Windsor, “Molecular Spectra and Molecular Structure,” Meeting, Columbus, Ohio, 1962.

Pavlopoulos, T.

M. A. El-Sayed and T. Pavlopoulos, “Polarization of the Triplet–Triplet Absorption Spectrum of Some Polyacenes,” J. Chem. Phys. (to be published).

Pringsheim, P.

P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949).

Ross, I.

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

Windsor, M. W.

R. S. Moore and M. W. Windsor, “Molecular Spectra and Molecular Structure,” Meeting, Columbus, Ohio, 1962.

J. Chem. Phys. (5)

D. S. McClure, J. Chem. Phys. 22, 1668 (1954).
[Crossref]

V. Krishna and L. Goodman, J. Chem. Phys. 36, 2217 (1962).
[Crossref]

V. Krishna and L. Goodman, J. Chem. Phys. 37, 912 (1962).
[Crossref]

D. S. McClure, J. Chem. Phys. 19, 670 (1951).
[Crossref]

A. Albrecht, J. Chem. Phys. 33, 156 (1960).
[Crossref]

J. Chem. Soc. (1)

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

J. Mol. Spectry. (1)

A. Albrecht, J. Mol. Spectry. 6, 84 (1961).
[Crossref]

Nature (2)

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

M. A. El-Sayed, Nature 197, 481 (1963).
[Crossref]

Trans. Faraday Soc. (1)

W. H. Melhuish and R. Hardwick, Trans. Faraday Soc. 58, 1908 (1962).
[Crossref]

Other (6)

R. S. Moore and M. W. Windsor, “Molecular Spectra and Molecular Structure,” Meeting, Columbus, Ohio, 1962.

P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949).

M. A. El-Sayed and R. G. Brewer, “Polarization of the π*→ π and π*→ n Phosphorescence Spectrum of Nitrogen Heterocyclics,” J. Chem. Phys. (to be published).

T. Förster, Fluoreszenz Organischer Verbindungen (Vandenhoech und Ruprecht, Göttingen, Germany, 1951).

P. P. Feofilov, The Physical Bases of Polarized Emission (Consultants Bureau, New York, 1961).

M. A. El-Sayed and T. Pavlopoulos, “Polarization of the Triplet–Triplet Absorption Spectrum of Some Polyacenes,” J. Chem. Phys. (to be published).

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Figures (2)

Fig. 1
Fig. 1

The optical arrangement used for measuring the polarization of the phosphorescence spectrum using the method of photoselection. (The names for the different components indicated by numbers here are given in the measurements section.)

Fig. 2
Fig. 2

The results on the polarization of the phenanthrene phosphorescence spectrum in plastic medium. The top spectra are obtained at liquid-nitrogen temperature and 1 mm thickness, while those at the bottom are obtained at room temperature and 5 mm thickness. IIl and IR indicate that the emission is obtained when the analyzer is in parallel and perpendicular position, respectively, with respect to the polarizer position.

Tables (1)

Tables Icon

Table I Comparison of the measured degree of polarization in plastic and glass media.