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Pressure Effects on the Photocycloaddition of 2-Adamantanone with Fumaronitrile

机译：压力对2-金刚烷酮与富马腈的光环加成反应的影响

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The photochemical (2+2) cycloaddition of 2-adamantanone (AD) with trans-dicyanoethylene (t-DCE was studied in acetonitrile as a function of pressure, and the activation volumes for both singlet and triplet reactions were determined. The competing reactions between excited singlet and triplet states of AD were found to be pressure dependent. At high pressure, the inte system crossing rate, kst, form singlet to triplet increased, and as a result the singlet lifetime of AD was shortened and the triplet reaction which leads to cis-trans isomerization of the starting olefin became favored as pressure was increased. The Stern-Volmer slopes were found to correlate linearly with solvent viscosity; however, the triplet reaction (kqt/kt) correlated linearly only with the solvent dielectric constant. Keywords: Pressure effects, Photochemistry, Intersystem crossing, Fluorescence quenching, Adamantanes, Reprints. (MJM)

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作者
Turro, N. J.; Chung, W. S.; Okamoto, M.;
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年度 1988
页码 p.1-12
总页数 12
原文格式 PDF
正文语种 eng
中图分类工业技术;
关键词
Acetonitrile; Adamantanes; Fluorescence; Photochemical reactions; Viscosity; Cyanides; Ethylene; Activation; Constants; Crossings; Dielectric properties; High pressure; Olefin polymers; Pressure; Quenching; Rates; Reprints; Solvents; Starting; Volume;

机译：乙腈;金刚烷;荧光;光化学反应;粘度;氰化物;乙烯;活化;常数;交叉;介电性能;高压;烯烃聚合物;压力;淬火;速率;重印;溶剂;起始;体积;

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1. Computational Studies of Chemical Shifts Using Density Functional Optimized Geometries. II. Isotropic ~H and ~13C Chemical Shifts and Substitutent Effects of ~13C Shieldings in 2-Adamantanone [J] . Drazen Vikic-Topic, Ljupco Pejov Croatica Chemica Acta . 2001,第2期

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2. Computational Studies of Chemical Shifts Using Density Functional Optimized Geometries. II. Isotropic sup1/supH and sup13/supC Chemical Shifts and Substitutent Effects on sup13/supC Shieldings in 2-Adamantanone [J] . Pejov Ljup?o, Viki?-Topi? Dra?en Croatica chemica acta . 2001,第2期

机译：使用密度泛函优化几何结构进行化学位移的计算研究。二。各向同性的 1 H和 13 C化学位移以及取代基对2-金刚烷酮 13 C屏蔽的影响
3. Pressure control of diastereodifferentiating [2 + 2] photocycloaddition of (E)-stilbene to chiral fumarate upon direct and charge-transfer excitation [J] . Hideaki Saito, Tadashi Mori, Takehiko Wada, Chemical Communications . 2004,第14期

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机译：压力对富马酸2-氨基偶氮酮的光催化作用

Pressure Effects on the Photocycloaddition of 2-Adamantanone with Fumaronitrile

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