G. Liu et al., PHOTOCHEMISTRY OF LOCALLY EXCITED AND INTRAMOLECULAR CHARGE-TRANSFER STATES OF (E)-4-CYANO-4'-(PENTAMETHYLDISILANYL)STILBENE, Journal of the American Chemical Society, 118(46), 1996, pp. 11412-11422
The photophysical properties and photochemistry of (E)-4-cyano-4'-(pen
tamethyldisilanyl) stilbene ((E)-3) and the corresponding monosilylate
d stilbene (E)-5 have been studied. Solvatochromic plots of (E)-3 show
separate slopes for ether solvents and halocarbons. The emission in e
thers is assigned to an LE state of similar polarity to that of(E)-5.
In halocarbons a more polar intramolecular charge transfer (CT) state
apparently contributes to the emission, This component is completely q
uenched by nucleophilic ethers, In contrast to (E)-5, Phi(f) and Phi(E
,Z) of (E)-3 strongly decrease in CH3CN, consistent with the solvent p
olarity induced LE --> CT process and nucleophilic quenching of the CT
state by solvent. Alcohols also quench Phi(f) and Phi(E,Z) with simil
ar Stern-Volmer constants, linking the two processes to the same state
(LE), Such quenching results in formation of (E)-4'-(hydrodimethylsil
yl)-4-cyanostilbene (4) by regioselective nucleophilic cleavage of the
Si-Si bond, according to deuterium labeling studies. Double reciproca
l plots of Phi(-1)(SiH) vs [ROH](-1) are consistent with both the LE a
nd CT states being quenched by ROH with the latter state giving (E)-4,
Quadratic behavior for MeOH in CH2Cl2 is ascribed to a solvent polari
ty promoted LE --> CT process with a rate constant proportional to [Me
OH], in accord with the linear relation of E(T)(30) vs In [MeOH] above
0.3 M MeOH. The quadratic behavior disappears in tert-amyl alcohol, w
hich has the same E(T)(30) as CH2Cl2. Results for MeOH in pentane sugg
est the LE and CT states have similar energies and interconvert.