Intramolecular Charge
Resonance in Dimer Radical Anions of Di-, Tri-, Tetra-, and Pentaphenylalkanes
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Abstract
Intramolecular dimer radical anions of di-, tri-, tetra-,
and pentaphenylalkanes were investigated on the basis of absorption
spectral measurements during γ-radiolysis in 2-methyltetrahydrofuran
(MTHF) glassy matrix at 77 K and theoretical calculations. The absorption
spectrum of 1,1,2,2-tetraphenylethane (1,1,2,2-Ph<sub>4</sub>E) radical
anion showed two bands in the near-infrared (NIR) region (900–2600
nm). One band observed at shorter wavelength than 2000 nm is assigned
to the intramolecular charge resonance (CR) band between two phenyl
groups of the 1,1-diphenylmethyl chromophore (1,1-dimer radical anion).
The intramolecular CR band of the 1,1-dimer radical anion was observed
for various alkanes having 1,1-diphenylmethyl chromophore such as
1,1,1-triphenylmethane (1,1,1-Ph<sub>3</sub>M), 1,1,1,1-tetraphenylmethane
(1,1,1,1-Ph<sub>4</sub>M), and so on. The other intramolecular CR
band observed at longer wavelength than 2200 nm is assigned to intramolecular
dimer radical anion between two phenyl groups of the 1,2-diphenylethyl
chromophore (1,2-dimer radical anion). The intramolecular CR band
of the 1,2-dimer radical anion was observed for various alkanes having
a 1,2-diphenylethyl chromophore, such as 1,1,2-triphenylethane (1,1,2-Ph<sub>3</sub>E), 1,1,2,2-Ph<sub>4</sub>E, and 1,1,1,2,2-pentaphenylethane
(1,1,1,2,2-Ph<sub>5</sub>E) and so on. No dimer radical anion was
observed for 1,<i>n</i>-diphenylalkanes (<i>n</i> > 2) without 1,1-diphenylmethyl chromophore. The relationship
between the structure and negative charge delocalization over two
phenyl groups connected by an sp<sup>3</sup> carbon is discussed