CAJ | 학술논문

用半经验AM1方法对苝二酸酐与嘧啶衍生物的1:1及1:2氢键复合物进行理论研究,表明随着氢键数目增多,弱相互作用能变大,主体上的供电基和客体上的吸电基有利于氢键相互作用,氢键导致电子从主体流向客体.用INDO/SCI方法计算配合物的电子光谱,表明其长波吸收峰与主体相比发生兰移,各配合物的长波吸收峰位置相差不大,与实验一致.讨论吸收峰兰移的原因并对电子跃迁进行理论指认,同时得到了配合物的双质子转移势能曲线,给出了相对于N-H键的过渡态和活化能.
용반경험AM1방법대패이산항여밀정연생물적1:1급1:2경건복합물진행이론연구,표명수착경건수목증다,약상호작용능변대,주체상적공전기화객체상적흡전기유리우경건상호작용,경건도치전자종주체류향객체.용INDO/SCI방법계산배합물적전자광보,표명기장파흡수봉여주체상비발생란이,각배합물적장파흡수봉위치상차불대,여실험일치.토론흡수봉란이적원인병대전자약천진행이론지인,동시득도료배합물적쌍질자전이세능곡선,급출료상대우N-H건적과도태화활화능.
Semi-empirical AM1 method was used to study 1:1 and 1:2 hydrogen bond complexes formed with perylene dianhydride and pyridine derivatives. The weak interaction energy become bigger as the number of hydrogen bonds increases. The donor groups on the host and electron-withdrawing groups on the guest molecules favor hydrogen bonding interactions, and the formation of hydrogen bonding leads to electron density flow from the host to the guest molecules. Electronic spectra of these complexes were computed using INDO/SCI method. Blue-shift of the electronic absorption spectra for the complexes, comparing that of the host,takes place, and the first peaks for different complexes changed slightly. These are in agreement with the experimental results. The cause of blue-shift was discussed, and the electronic transitions were assigned based on theoretical calculations. The potential curve of double proton transfer in the complex was calculated, and the transition state and activated energy relative to the N-H bond were obtained.