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Photochemistry and Photophysics of Organosilicon Compounds

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Photochemical and photophysical processes of organosilicon compounds have been studied. Dual (local and CT) emission has been found in aromatic disilanes. The intramolecular CT fluorescence has a broad and structureless band with a large Stokes shift. The CT process in the excited state occurs very rapidly with a time constant less than 10 ps even in rigid glass at 77 K. This finding shows that the CT mechanism is quite different from TICT (or OICT) which needs twisting or internal rotation during the lifetime in the excited state. The CT emission originates from the 1(2pπ,3dπ) state having an in-plane long-axis polarization, which is produced by the 2pπ* (aromatic ring) → vacant 3dπ (Si-Si bond) intramolecular charge transfer. The CT state plays an important role in the photochemical and photophysical properties of phenyldisilanes. At room temperature a long-lived 425 nm transient (silene) is produced with a time constant of 30 ps from the CT state. The photolysis of cyclotetrasilanes is remarkably dependent on their molecular structures: two molecules of the corresponding disilene are produced from the S1 state of planar

Affiliations: 1: Department of Chemistry Gunma University Kiryu, Gunma 376, JAPAN


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