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Photoisomerization of norbornadiene group in a rigid bichromophoric compound initiated by remote keto chromophore: long-distance through-bond triplet energy transfer

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Chinese Journal of Chemistry 1996年第4期14卷 377-380页

作者： Tung, CH Zhang, LP Li, Y CHINESE ACAD SCI INST PHOTOG CHEMBEIJING 100101PEOPLES R CHINA

A diad compound 3 beta(bicyclo[2,2,1]hepta-2,5-diene-2-methylcarboxylate-3-carboxy)-androst-5-en-17-one (NBD-S-ONE) was synthesized and its photochemistry was examined. Irradiation of NBD-S-ONE in acetonitrile at lambda > 300 nm selectively excited the keto chromophore. After intersystem crossing, the triplet energy of the keto group was transferred to the NBD group with 18.6% efficiency via a through-bond mechanism, resulting in the isomerization of the latter group to the quadricyclane group.

关键词： norbornadiene photoisomerization through-bond triplet energy transfer

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Oxidation of norbornadiene:Theoretical investigation on H-atom abstraction and related radical decomposition reactions

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Propulsion and Power Research 2023年第1期12卷 104-113页

作者： Jintao Chen Mingxia Liu Yuxiang Zhu Kairu Jin Zhenyu Tian Lijun Yang Chong-Wen Zhou School of Energy and Power Engineering Beihang UniversityBeijing 100191China Institute of Engineering Thermophysics Chinese Academy of SciencesBeijing 100190China University of Chinese Academy of Sciences Beijing 100049China School of Astronautics Beihang UniversityBeijing 100191China Combustion Chemistry Centre School of Biological and Chemical SciencesUniversity of GalwayGalway H91TK33Ireland

The chemical kinetics of hydrogen atom(H-atom)abstraction reactions from norbornadiene(NBD)by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2)),and the unimolecular reactions of three NBD derived radicals,were studied through high-level ab-initio *** geometries optimization and vibrational frequencies calculation for all the reactants,transition states,and products were obtained at the M06-2X/6-311ttG(d,p)level of *** zeropoint energy(ZPE)corrected potential energy surfaces(PESs)were determined at the QCISD(T)/cc-pVDZ,TZ level of theory with basis set corrections from MP2/cc-pVDZ,TZ,QZ methods for single point energy *** transition state theory(TST)was used for the rate constants calculations of H-atom abstraction reactions by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2))at temperatures from 298.15 to 2000 K,while the a-site H-atom abstraction reaction rate constant of NBD by OH radical has been obtained through variational transition state theory(VTST).The results show that the H-atom abstraction reactions from the α-carbon atom of NBD are the most critical channels at low *** rate constants for H-atom abstraction reactions by OH radical are also the fastest among all of the reaction channels investigated at the temperature range from 298.15 to 2000 ***-Ramsperger-Kassel-Marcus/Master Equation(RRKM/ME)has been used to calculate the pressure-and temperature-dependent rate constants for the unimolecular reactions of three related C7H7 product radicals which generated from H-atom abstraction reaction within temperature ranges of 300-2000 K and pressures of 0.01-100 atm.A combination of composite methods has been used to calculate the temperature-dependent thermochemical properties of NBD and related *** the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation.

关键词： norbornadiene Ab-initio calculations Rate constants Kinetic Thermochemistry

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