scholarly journals Does diphenylacetylene (tolan) fluoresce from its second excited singlet state? Semiempirical MO calculations and fluorescence quantum yield measurements

1993 ◽  
Vol 97 (51) ◽  
pp. 13457-13463 ◽  
Author(s):  
Camilla Ferrante ◽  
Uwe Kensy ◽  
Bernhard Dick

1980 ◽  
Vol 35 (12) ◽  
pp. 1411-1414 ◽  
Author(s):  
D. Gloyna ◽  
A. Kawski ◽  
I. Gryczyński

AbstractThe effect of substituents on the fluorescence quantum yield φf of trans-stilbenes (1) in dimethylformamide, acetonitrile, and n-propanol, as well as in n-heptane, is mainly due to radiationless deactivation. Contrary to n-heptane, the rate kd of radiationless deactivation in the above mentioned polar solvents for compounds 1 of similar structure is not a monotoneous function of the polarity of the first excited singlet state. The maximum of kd corresponds to compounds with medium polarity (1h, 1i). The effect of substituents on the fluorescence rate kfn in polar and nonpolar solvents is small compared to that on kd. In all solvents kfn drops with increasing polarity of the first excited singlet state.



1968 ◽  
Vol 46 (14) ◽  
pp. 2353-2360 ◽  
Author(s):  
A. N. Strachan ◽  
D. E. Thornton

Ketene has been photolyzed at 3660 and 3130 Å both alone and in the presence of the inert gases C4F8 and SF6. The quantum yield of carbon monoxide has been determined at both wavelengths as a function of pressure and temperature. At 3660 Å the quantum yield decreases with increasing pressure but increases with increasing temperature. At 3130 Å the quantum yield with ketene alone remains 2.0 at both 37 and 100 °C at pressures up to 250 mm. At higher pressures of ketene or with added inert gas the quantum yield decreases with increasing pressure. The results are interpreted in terms of a mechanism in which intersystem crossing from the excited singlet state to the triplet state occurs at both wavelengths, and collisional deactivation of the excited singlet state by ketene is single stage at 3660 Å but multistage at 3130 Å.



The value of k 6 /( k 4 + k 5 + k 6 ) (mechanism of part I) was determined by two techniques, namely the sensitization of the isomerization of cis - to trans -butene-2 and the sensitization of the phosphorescence of biacetyl. Both techniques yielded a value for the ratio of 0⋅9 ± 0⋅1. The value obtained by the isomerization technique is a lower limit because the quantum yield for the isomerization did not attain a value independent of [ cis -butene-2], but reached a maximum at low concentrations of olefine and then decreased. A similar scavenging of the excited singlet state of hexafluoroacetone was observed when biacetyl was present as an addend. However, in both cases the measurements were made with sufficiently low concentrations of addend that the singlet scavenging should have introduced less, than 10% error. It is concluded that reaction (5) of the mechanism cannot be an important mode of disappearance of excited ketone molecules.



1980 ◽  
Vol 58 (21) ◽  
pp. 2230-2235 ◽  
Author(s):  
Louise-Marie Coulangeon ◽  
Gilles Perbet ◽  
Pierre Boule ◽  
Jacques Lemaire

The dual fluorescence observed in aqueous solution of o-phenyl-phenol is attributed to a deprotonation equilibrium in the excited singlet state. The effect of oxygen on the primary photochemical process of formation of phenoxy radicals can be explained in a parallel study of the variations of fluorescence and photo-oxidation quantum yields of this phenolic compound at different pH. It is shown that photoionisation occurs only from the excited singlet state of the phenolate form. Oxygen inhibits recombination of the solvated electron and phenoxy radical. Increase of quantum yield for the disappearance of irradiated o-phenyl-phenol in degased solution also is observed in the presence of electron scavengers like Cd2+ or NO3− ions. Even when the phenoxy radicals are not able to react with oxygen, quantum yield for the disappearance of the phenolic compounds is higher in an aerated than in a degassed solution; the oxygen effect on the primary photochemical step may explain this difference.



2002 ◽  
Vol 76 (1) ◽  
pp. 47 ◽  
Author(s):  
Joakim Andréasson ◽  
Gerdenis Kodis ◽  
Su Lin ◽  
Ana L. Moore ◽  
Thomas A. Moore ◽  
...  




2017 ◽  
Vol 122 (1) ◽  
pp. 130-139
Author(s):  
Jordan A. Greco ◽  
Nicole L. Wagner ◽  
Harry A. Frank ◽  
Robert R. Birge


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