Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL), University of Castilla-La Mancha Campus de la Fábrica de Armas, Toledo 45072, Spain.
Chemistry. 2012 Jun 11;18(24):7473-85. doi: 10.1002/chem.201102260. Epub 2012 May 3.
Donor-bridge-acceptor triad (Por-2TV-C(60)) and tetrad molecules ((Por)(2)-2TV-C(60)), which incorporated C(60) and one or two porphyrin molecules that were covalently linked through a phenylethynyl-oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto- and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C(60) moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C(60) moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C(60). Then, back-electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)-2TV-C(60) and (Por)(2)-2TV-C(60) acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C(60).
供体-桥-受体三联体（Por-2TV-C(60)) 和四联体分子((Por)(2)-2TV-C(60)) 被合成，其中包含 C(60) 和一个或两个通过苯乙炔-寡聚噻吩亚乙烯桥共价连接的卟啉分子。通过荧光测量和飞秒和纳秒激光闪光光解研究了它们的光动力学。首先，从卟啉到 C(60)部分发生光诱导能量转移，而不是电子转移，然后从寡聚噻吩亚乙烯转移电子到 C(60)部分的单重激发态，产生寡聚噻吩亚乙烯的自由基阳离子和 C(60)的自由基阴离子。然后，发生反向电子转移以提供寡聚噻吩亚乙烯部分的三重激发态而不是基态。因此，(Por)-2TV-C(60) 和 (Por)(2)-2TV-C(60) 中的卟啉单元充当了寡聚噻吩亚乙烯和 C(60)之间电荷分离的有效光致敏化剂。
