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Discussion A general trend which appears evident in the data is that radiative and radiationless rate constants increase as the polarity of the solvent increases. If the increasing radiationless process is intersystem crossing to the triplet then more phosphorescence is expected in polar solvents. On the other hand, if the increasing ratiationless process is internal conversion, Le., S1 -+ So, then more phosphorescence is expected in nonpolar solvents. The fact that the fluorescence yield generally increases in more polar solvents is readily accounted for by the increasing value of k ~Fu. rt hermore, the observation that the phosphorescence of these molecules is present in polar solvents, but absent in nonpolar solvents such as methylcyclohexane strongly suggests that the radiationless mode which exhibits enhancement in polar solvents is intersystem crossing. Thus the observation that $JF and $Jp increase with solvent polarity suggests that hi, (internal conversion) becomes less important or alternatively that hi, is approximately constant at-4 X lo7 s-l, i.e., in cyclohexane h& ki, since intersystem crossing is unimportant. |
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