Departamento de Química e QOPNA, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal.
Chemistry. 2012 Mar 12;18(11):3210-9. doi: 10.1002/chem.201103776. Epub 2012 Feb 13.
The synthesis and photophysical properties of several porphyrin (P)-phthalocyanine (Pc) conjugates (P-Pc; 1-3) are described, in which the phthalocyanines are directly linked to the β-pyrrolic position of a meso-tetraphenylporphyrin. Photoinduced energy- and electron-transfer processes were studied through the preparation of H(2)P-ZnPc, ZnP-ZnPc, and PdP-ZnPc conjugates, and their assembly through metal coordination with two different pyridylfulleropyrrolidines (4 and 5). The resulting electron-donor-acceptor hybrids, which were formed by axial coordination of compounds 4 and 5 with the corresponding phthalocyanines, mimicked the fundamental processes of photosynthesis; that is, light harvesting, the transduction of excited-state energy, and unidirectional electron transfer. In particular, photophysical studies confirmed that intramolecular energy-transfer resulted from the S(2) excited state as well as from the S(1) excited state of the porphyrins to the energetically lower-lying phthalocyanines, followed by an intramolecular charge-transfer to yield P-Pc(.+)⋅C(60)(.-). This unique sequence of processes opens the way for solar-energy-conversion processes.
几种卟啉（P）-酞菁（Pc）缀合物（P-Pc；1-3）的合成和光物理性质被描述，其中酞菁直接连接到间四苯基卟啉的β-吡咯位置。通过制备 H（2）P-ZnPc、ZnP-ZnPc 和 PdP-ZnPc 缀合物，并通过与两个不同的吡啶基富勒烯吡咯烷（4 和 5）的金属配位来研究光诱导的能量和电子转移过程。通过化合物 4 和 5 与相应的酞菁的轴向配位形成的电子给体-受体杂化物模拟了光合作用的基本过程；即，光的吸收、激发态能量的传递和单向电子转移。特别地，光物理研究证实，分子内能量转移来自于卟啉的 S（2）激发态以及 S（1）激发态到能量较低的酞菁，随后是分子内电荷转移以产生 P-Pc（.+）⋅C（60）（.-）。这个独特的过程序列为太阳能转换过程开辟了道路。
