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Delayed Luminescence of Organic Mixed Crystals. VI. Delayed Excimer Fluorescence of Pyrene in Biphenyl

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1701764· OSTI ID:2473061
 [1];  [1];  [1]
  1. Coates Chemical Laboratories, Louisiana State University, Baton Rouge, Louisiana
Phosphorescence, fluorescence, delayed fluorescence, excimer fluorescence, and delayed excimer fluorescence of pyrene have been studied in a host biphenyl system. The delayed fluorescence and delayed excimer fluorescence are biexcitonic, have identical lifetimes at all temperatures and exhibit similar dependency of emission intensity on temperature; therefore, they both originate in identical kinetic events. These events involve thermal depletion of a trap of energy ∼1000 cm−1 less than the lowest energy host exciton triplet band and of lifetime ∼0.2 sec; this trap species may or may not be, but probably is not, a contaminant detected phosphorimetrically in the purified biphenyl material. It appears that trapping of the host triplet exciton occurs more efficiently at monomer pyrene sites than at nascent excimeric pyrene sites (regions, perhaps, of pyrene microcrystallinity). The excimer and delayed excimer fluorescence exhibit vibrational structure under certain circumstances; this structure is analyzable in terms of ag modes of the ground-state monomeric pyrene. Those crystals which possess broad (i.e., unresolved) excimer spectra exhibit a distinct red shift of this spectrum as the temperature is decreased; this behavior is rationalized herein. The guest phosphorescence intensity and lifetime are more or less temperature-independent; this behavior is quite characteristic of materials with large T1H—T1G bandgaps. Excitation spectra for all emissions are presented; it is shown thereby that trap species other than T1G are the reservoir whence thermal excitation to the host exciton band T1H proceeds. The thesis developed is that delayed excimer fluorescence and delayed fluorescence are produced by annihilation of a trap triplet and a guest triplet.
Research Organization:
Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Organization:
US Atomic Energy Commission (AEC)
OSTI ID:
2473061
Report Number(s):
ORO--3018-3
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 47; ISSN 0021-9606
Country of Publication:
United States
Language:
English

References (17)

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Concentration dependence of quantum yield of triplet-state production of pyrene in ethanol journal January 1966
Delayed Fluorescence of Mixed Crystals journal May 1965
Delayed Excimer Fluorescence of Pyrene journal June 1965
Energy of Excimer Luminescence. III. Group Theoretical Considerations of Molecular Exciton and Charge Resonance States journal March 1965
Excited Dimer (Excimer) Luminescence from Aromatic Molecules in Crystalline Cyclohexane journal July 1965
Spectral Shifts in the Absorption and Fluorescence of Pyrene under High Pressures journal December 1965
Polarized Fluorescence of Molecules of Some Single Organic Crystals journal March 1953
Investigation of Triplet-State Energy Transfer in Organic Single Crystals by Magnetic Resonance Methods journal April 1965
Energy of Excimer Luminescence. II. Configuration Interaction between Molecular Exciton States and Charge Resonance States journal December 1964
Investigation of Triplet-State Energy Transfer and Triplet—Triplet Annihilation in Organic Single Crystals by Magnetic Resonance and Emission Spectra: Diphenyl Host journal November 1965
Delayed Luminescence of Organic Mixed Crystals journal May 1966
Delayed Luminescence of Organic Mixed Crystals. III. Decay Characteristics journal August 1966
Radiationless Transitions: A Semiclassical Model journal June 1962
Triplet—Triplet Annihilation and Delayed Fluorescence in Molecular Aggregates journal March 1963
Absorption and Fluorescence Spectra of Crystalline Pyrene journal May 1958
Fine structure in excimer emission journal September 1965

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