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首页> 美国政府科技报告 >Investigations of the Influence of Molecular Geometry on the Spectroscopic and Photochemical Properties of Alpha-Oxo(1.n)Paracyclophanes (Cyclophanobenzophenones).
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Investigations of the Influence of Molecular Geometry on the Spectroscopic and Photochemical Properties of Alpha-Oxo(1.n)Paracyclophanes (Cyclophanobenzophenones).

机译：分子几何对α-氧代（1.n）对环芳烷（环苯并二苯甲酮）光谱和光化学性质影响的研究。

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摘要

The spectroscopic and photochemical properties of a family of alpha-oxo (1,n) paracyclophanes (8-12) for n=8-12, respectively) have been investigated. Compared to a model structure possessing a nominal T1 (n, Pi*) state (4,4'-dimethylbenzophenone, DM-BZ), photochemical and photophysical evidence is presented that the n(Pi*) character of T1 decreases as the cyclophane ring size decreases. For example, the rate constants for hydrogen atom abstraction from 1,4-cyclohexadiene in acetonitrile are 1.6 x 10 to the 8th power, 0.93 x 10 to the 8th power, 0.06 x 10 to the 8th power, and 0.04 x 10 to the 8th power/m/s for triplet 12-8 respectively, a result consistent with decreasing n(pi*) character and decreasing reactivity toward hydrogen atom abstraction with decreasing value of n. The spectroscopic properties (vibrational structure of the phosphorescence spectrum, phosphorescence lifetime, phosphorescence excitation spectra, triplet-triplet absorption spectra) also vary in a manner consistent with decreasing n(pi*) character as the cyclophane ring size decreases. Reprints. (AW)

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