Self-Assembly of Supramolecular Light-Harvesting Arrays from Covalent Multi-Chromophore Perylene-3,4:9,10-bis(dicarboximide) Building Blocks

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• 作者：Michael J. Ahrens ; Louise E. Sinks ; Boris Rybtchinski ; Wenhao Liu ; Brooks A. Jones ; Jovan M. Giaimo ; Alexy V. Gusev ; Andrew J. Goshe ; David M. Tiede ; and Michael R. Wasielewski
• 刊名：Journal of the American Chemical Society
• 出版年：2004
• 出版时间：July 7, 2004
• 年：2004
• 卷：126
• 期：26
• 页码：8284 - 8294
• 全文大小：392K
• 年卷期：v.126,no.26(July 7, 2004)
• ISSN：1520-5126

文摘

We report on two multi-chromophore building blocks that self-assemble in solution and on surfacesinto supramolecular light-harvesting arrays. Each building block is based on perylene-3,4:9,10-bis(dicarboximide) (PDI) chromophores. In one building block, N-phenyl PDI chromophores are attached at theirpara positions to both nitrogens and the 3 and 6 carbons of pyromellitimide to form a cross-shaped molecule(PI-PDI₄). In the second building block, N-phenyl PDI chromophores are attached at their para positions toboth nitrogens and the 1 and 7 carbons of a fifth PDI to produce a saddle-shaped molecule (PDI₅). Thesemolecules self-assemble into partially ordered dimeric structures (PI-PDI₄)₂ and (PDI₅)₂ in toluene and2-methyltetrahydrofuran solutions with the PDI molecules approximately parallel to one another primarilydue to - interactions between adjacent PDI chromophores. On hydrophobic surfaces, PDI₅ grows intorod-shaped nanostructures of average length 130 nm as revealed by atomic force microscopy. Photoexcitation of these supramolecular dimers in solution gives direct evidence of strong - interactionsbetween the excited PDI chromophore and other PDI molecules nearby based on the observed formationof an excimer-like state in <130 fs with a lifetime of about 20 ns. Multiple photoexcitations of thesupramolecular dimers lead to fast singlet-singlet annihilation of the excimer-like state, which occurs withexciton hopping times of about 5 ps, which are comparable to those observed in photosynthetic light-harvesting proteins from green plants.