期刊
CHEMICAL COMMUNICATIONS
卷 48, 期 79, 页码 9801-9815出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cc32848h
关键词
-
资金
- MEXT [20108010, 23750014]
- U.S. NSF [CHE 1057904, CHE 1110942]
- R.A. Welch Foundation [F-1018]
- KOSEF/MEST through WCU projects, Korea [R31-2008-000-10010-0, R32-2010-000-10217-0]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1110942] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1057904] Funding Source: National Science Foundation
- Grants-in-Aid for Scientific Research [20108010, 23750014] Funding Source: KAKEN
Anion binding has emerged as an attractive strategy to construct supramolecular electron donor-acceptor complexes. In recent years, the level of sophistication in the design of these systems has advanced to the point where it is possible to create ensembles that mimic key aspects of the photoinduced electron-transfer events operative in the photosynthetic reaction centre. Although anion binding is a reversible process, kinetic studies on anion binding and dissociation processes, as well as photoinduced electron-transfer and back electron-transfer reactions in supramolecular electron donor-acceptor complexes formed by anion binding, have revealed that photoinduced electron transfer and back electron transfer occur at time scales much faster than those associated with anion binding and dissociation. This difference in rates ensures that the linkage between electron donor and acceptor moieties is maintained over the course of most forward and back electron-transfer processes. A particular example of this principle is illustrated by electron-transfer ensembles based on tetrathiafulvalene calix[4] pyrroles (TTF-C4Ps). In these ensembles, the TTF-C4Ps act as donors, transferring electrons to various electron acceptors after anion binding. Competition with non-redox active substrates is also observed. Anion binding to the pyrrole amine groups of an oxoporphyrinogen unit within various supramolecular complexes formed with fullerenes also results in acceleration of the photoinduced electron-transfer process but deceleration of the back electron transfer; again, this is ascribed to favourable structural and electronic changes. Anion binding also plays a role in stabilizing supramolecular complexes between sulphonated tetraphenylporphyrin anions ([MTPPS](4-) : M = H-2 and Zn) and a lithium ion encapsulated C-60 (Li+ @ C-60); the resulting ensemble produces long-lived charge-separated states upon photoexcitation of the porphyrins.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据