北醌及其衍生物分子内氢转移的机理与光敏活性

HF/CIS methods were carried out to study the intramolecular hydrogen transfer(IHT) of perylenequinone both in the ground and excited states according to the previous project. We got many delightful results such as reaction barrier and rate constant and so on. We can make the primary conclusion that the IHT process of perylenequinone and its derivatives is a single hydrogen transfer process not a concerted process. A novel type of perylenequinone its derivatives-Hypomycin B (HMB) and its model compounds was calculated for the first time. It is found that the energy of these systems and barriers for IHT reaction are mainly determined by the conjugation structure or the resonance mode. The side-chain and side ring have little influence on the barrier of HMB's IHT. The barrier is linear to the change of the atom's charge for most similar systems, and linear to the change of the H-bond length or hydroxyl O-H bond length. Potential energy surface of IPT in the S1 and T1 excited states display crossings, and this single IPT process enhances the intersystem crossing (ISC) of singlet-excited molecule. The ISC will increase triplet quantum efficiency, which is the basis for photosensitization of PQP

用高水平的量子化学方法，在包含溶剂效应和包略溶剂效应两种条件下，计算研究PQ分子内氢转移反应的势能面以及激发态吸收光谱等，研究共轭效应、取代基效应对IHT过程的影响蛔詈笥谩翱瞻资笛榉ā鄙杓埔幌盗心Ｐ突衔铮源搜芯縄HT过程与光敏活性的内在联系。该项目将对PQD的IHT过程进行系统的阐释，为设计新型的高光敏活性的分子奠定基础。.