光引发有机分子电子转移和氢转移反应研究-物理化学专业论文.docxVIP

摘要 关键词:激光闪光光解 唾吨酣 5，12-荼并荼 电子转移 氢转移 11 A A bstract A BSTRACT Time—resolved laser flash photolysis is a technique used tO distinguish the transient species of photochemistry systems．From changes of the transient absorption spectra and the kinetic constants(such as quenching rate constants and free energy changes)，the mechanism of the reactions can be infered．The fast reactions of the organic molecules are studied by our homemade laser flash photolysis instrument．The results are as follow： 1．The transient absorption spectra and the quenching rate constants of the excited thioxanthone(TX)by a series of amines，phenols and alcohols were received．From changes of the absorption spectra，we infer that electron transfer reactions occur between TX and amines without active hydrogen such as TPA and DABCO，while the electron／proton transfer reactions occur between TX and amines with active hydrogen， such as DMT，TMA，DPA．For only appearance of the ketyl radical，we conclude that charge／hydrogen transfer reactions happen in TX／phenols systems and direct hydrogen transfer reactions happen in TX／alcohols systems．Due to different hydrogen transfer mechanism，quenching rate constants are larger in TX／phenols systems than in TX／alcohols systems．In TX／amines systems，quenching rate constants decrease following the increasing of the free energy changes(AG)．Whereas，in TX／phenols systems，quenching rate constants increase along with the increasing of the phenols cations’acidities，which can be explained that charge and hydrogen transfer may play an important role separately．With the increasing of the Q—C—H bonding energy of alcohols，the quenching rate constants decrease in the TX／alcohols systems，which indicate a·C-H bonding energy is the key factor for the triplet TX quenching． Comparing with the previous studies of the quenching reactions of triplet xanthone(XT)，fluorenone(FL)by a series of amines，phenols and alcohols，it is known that discrepancy of the molecule configuration influenc