Influence of Supramolecular Organization on Energy Transfer Properties in Chiral Oligo(p-phenylene vinylene) Porphyrin Assemblies

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• 作者：Freek J. M. Hoeben ; Martin Wolffs ; Jian Zhang ; Steven De Feyter ; Philippe Leclè ; re ; Albertus P. H. J. Schenning ; E. W. Meijer
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：August 8, 2007
• 年：2007
• 卷：129
• 期：31
• 页码：9819 - 9828
• 全文大小：544K
• 年卷期：v.129,no.31(August 8, 2007)
• ISSN：1520-5126

文摘

A comparative study on oligo(p-phenylene vinylene) (OPV)-appended porphyrins containing alltrans-vinylene (either hydrophilic or lipophilic) or amide linkages (lipophilic) is presented. The type ofsupramolecular arrangement obtained in organic solvents proves to be strongly dependent on the natureof the covalent connection. In the case of all trans-vinylene linkages, a J-type intermolecular packing isobtained and the assemblies are only of moderate stability. Conversely, the supramolecular structuresobtained from the amide-linked system display an H-type stacking arrangement of enhanced stability andchirality as a consequence of intermolecular hydrogen bonding along the stack direction, favorablyinterlocking the stacked building blocks. Interestingly, the observed differences in stability and organizationare qualitatively illustrated by monitoring the sequential energy transfer process in both types of assemblies.Efficient intramolecular energy transfer from the OPVs (donors) to the respective porphyrin cores is followedby energy transfer from Zn-porphyrin (donor) to free-base porphyrin (acceptor) in both systems. However,the improved intermolecular organization for the amide-linked system increases the energy transfer efficiencyalong the stack direction. In addition, the water-soluble (OPV)-appended porphyrin system forms highlystable assemblies in an aqueous environment. Nevertheless, the poor energy transfer efficiency along thestack direction reveals a relative lack of organization in these assemblies.