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• W2002057874 abstract "The photophysical properties and photochemistry of (E)-4-cyano-4‘-(pentamethyldisilanyl)stilbene ((E)-3) and the corresponding monosilylated stilbene (E)-5 have been studied. Solvatochromic plots of (E)-3 show separate slopes for ether solvents and halocarbons. The emission in ethers 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 quenched by nucleophilic ethers. In contrast to (E)-5, Φf and Φ(E,Z) of (E)-3 strongly decrease in CH3CN, consistent with the solvent polarity induced LE → CT process and nucleophilic quenching of the CT state by solvent. Alcohols also quench Φf and Φ(E,Z) with similar Stern−Volmer constants, linking the two processes to the same state (LE). Such quenching results in formation of (E)-4‘-(hydrodimethylsilyl)-4-cyanostilbene (4) by regioselective nucleophilic cleavage of the Si−Si bond, according to deuterium labeling studies. Double reciprocal plots of Φ-1(SiH) vs [ROH]-1 are consistent with both the LE and CT states being quenched by ROH with the latter state giving (E)-4. Quadratic behavior for MeOH in CH2Cl2 is ascribed to a solvent polarity promoted LE → CT process with a rate constant ∝ [MeOH], in accord with the linear relation of ET(30) vs ln [MeOH] above 0.3 M MeOH. The quadratic behavior disappears in tert-amyl alcohol, which has the same ET(30) as CH2Cl2. Results for MeOH in pentane suggest the LE and CT states have similar energies and interconvert." @default.
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• W2002057874 date "1996-01-01" @default.
• W2002057874 modified "2023-09-27" @default.
• W2002057874 title "Photochemistry of Locally Excited and Intramolecular Charge Transfer States of (<i>E</i>)-4-Cyano-4‘-(pentamethyldisilanyl)stilbene" @default.
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• W2002057874 doi "https://doi.org/10.1021/ja962218k" @default.
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