PREPARATION AND PHOTOPHYSICAL STUDIES OF PORPHYRIN‐C60 DYADS
PREPARATION AND PHOTOPHYSICAL STUDIES OF PORPHYRIN‐C60 DYADS
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卟啉-C60 二元体的制备和光物理研究
DOI：
10.1111/j.1751-1097.1994.tb05145.x
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发表时间：
1994
影响因子：
3.3
通讯作者：
D. Gust
中科院分区：
文献类型：
--
作者：
P. Liddell;J. Sumida;A. N. Macpherson;Lori Noss;G. R. Seely;Kristine N. Clark;A. Moore;T. Moore;D. Gust
摘要利用Diels-桤木反应合成了两个发色团通过双环桥连接的卟啉-C60二联体。通过时间分辨荧光测量确定的锌（Pzn-C60）和游离碱（P-C60）二联体的卟啉单重态寿命在甲苯中为1017 ps。Pzn-1C 60在甲苯中的寿命为-5 ps，而适当的C60模型化合物的单重态寿命为1.2 ns。这种淬灭归因于电子转移以产生Pznbull;+-C60 bull;-。在甲苯中，P-1C 60是未淬灭的;缺乏电子转移是由于不利的热力学。在该溶剂中，使用瞬态吸收方法检测到瞬态，吸收最大值为700 nm，寿命为-10 μs。该状态被氧淬灭，并被归属于C60三重态。在更极性的苄腈中，P-1C 60在光诱导电子转移下产生P·+-C60 bull;-。电子转移速率常数为−2 × 1011 s−1。
Abstract Porphyrin‐C60 dyads in which the two chromophores are linked by a bicyclic bridge have been synthesized using the Diels‐Alder reaction. The porphyin singlet lifetimes of both the zinc (Pzn‐C60) and free base (P‐C60) dyads, determined by time‐resolved fluorescence measurements, are ≦17 ps in toluene. This substantial quenching is due to singlet‐singlet energy transfer to C60 The lifetime of Pzn‐1C60 is ‐5 ps in toluene, whereas the singlet lifetime of an appropriate C60 model compound is 1.2 ns. This quenching is attributed to electron transfer to yield Pznbull;+‐C60bull;‐. In toluene, P‐1C60 is unquenched; the lack of electron transfer is due to unfavorable thermodynamics. In this solvent, a transient state with an absorption maximum at 700 ran and a lifetime of‐10 μs was detected using transient absorption methods. This state was quenched by oxygen, and is assigned to the C60 triplet. In the more polar benzonitrile, P‐1C60 underoes photoinduced electron transfer to give P•+‐C60bull;‐. The electron transfer rate constant is −2 × 1011 s−1.