Aoki Toru, Sakai Hayato, Ohkubo Kei, Sakanoue Tomo, Takenobu Taishi, Fukuzumi Shunichi, Hasobe Taku
Department of Chemistry , Faculty of Science and Technology , Keio University , Yokohama , 223-8522 , Japan . Email:
Department of Material and Life Science , Graduate School of Engineering , Osaka University , ALCA , Japan Science and Technology Agency (JST) , Suita , Osaka 565-0871 , Japan . Email:
Chem Sci. 2015 Feb 2;6(2):1498-1509. doi: 10.1039/c4sc02787f. Epub 2014 Nov 28.
Charge-transfer (CT) π-complexes are formed between planar porphyrins and 1,4,5,8,9,12-hexaazatriphenylene (HAT) derivatives with large formation constants (, 10 M), exhibiting broad CT absorption bands. The unusually large formation constants result from close face-to-face contact between two planar π-planes of porphyrins and HAT derivatives. The redox potentials of porphyrins and HAT derivatives measured by cyclic voltammetry indicate that porphyrins and HAT derivatives act as electron donors and acceptors, respectively. The formation of 1 : 1 CT complexes between porphyrins and HAT derivatives was examined by UV-vis, fluorescence and H NMR measurements in nonpolar solvents. The occurrence of unprecedented ultrafast photoinduced electron transfer from the porphyrin unit to the HAT unit in the CT π-complex was observed by femtosecond laser flash photolysis measurements. A highly linear aggregate composed of a planar porphyrin and an HAT derivative was observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM).
电荷转移（CT）π络合物是在平面卟啉与1,4,5,8,9,12 - 六氮杂三亚苯（HAT）衍生物之间形成的，其形成常数很大（，10 M），呈现出宽的CT吸收带。异常大的形成常数源于卟啉和HAT衍生物的两个平面π平面之间紧密的面对面接触。通过循环伏安法测量的卟啉和HAT衍生物的氧化还原电位表明，卟啉和HAT衍生物分别作为电子供体和受体。在非极性溶剂中，通过紫外可见光谱、荧光光谱和核磁共振氢谱测量研究了卟啉与HAT衍生物之间1∶1 CT络合物的形成。通过飞秒激光闪光光解测量观察到在CT π络合物中发生了前所未有的从卟啉单元到HAT单元的超快光诱导电子转移。通过透射电子显微镜（TEM）和原子力显微镜（AFM）观察到由平面卟啉和HAT衍生物组成的高度线性聚集体。
