Journal of Physical Chemistry p. 143 - 149 (1993)
Update date:2022-07-30
Topics:
Ruberu, Shiyamalie
Fox, Marye Anne
The excitation of perchlorodiphenylmethyl radical (PDM) at 530 nm leads to the lowest excited doublet, D1 (τ = 31 ns), from which emission is observed (Φ = 1 x 10-3 +/- 0.0003).This state is quenched by electron donors and acceptors at a rate at or close to diffusion control and at much slower rates by oxygen and hydrogen atom donors.Fragmentation of PDM (Φd = 0.06) occurs from a higher excited doublet (Dn, n > = 2) producing intermediates that are trapped by O2, chlorine, or hydrogen donors, yielding products 1-6.Experimental evidence suggests a structure-photoreactivity correlation in the perchlorinated arylmethyl radicals in which the partitioning between photochemical cyclization or fragmentation depends on the twist angle between the appended phenyl rings.
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