Chiral self-discriminative self-assembling of meso–meso linked diporphyrins

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• 作者：Chihiro Maeda ; Taisuke Kamada ; Naoki Aratani ; Atsuhiro Osuka
• 关键词：Porphyrin ; Self-sorting ; Self-assembly ; Chiral recognition
• 刊名：Coordination Chemistry Reviews
• 出版年：2007
• 出版时间：November 2007
• 年：2007
• 卷：251
• 期：21-24
• 页码：2743-2752
• 全文大小：1381 K

文摘

We have explored a variety of self-assembled cyclic porphyrin arrays mainly as biomimetic models of light harvesting antenna in photosynthetic systems. The key reaction is Ag(I)-promoted coupling reaction of 5,15-diaryl zinc(II) porphyrin that provides a meso–meso linked diporphyrin. meso-Pyridine-appended zinc(II) porphyrins M1–M3 and their meso–meso linked dimers D1–D3 assemble spontaneously in non-coordinating solvents into tetrameric porphyrin squares S1–S3 and porphyrin boxes B1–B3, respectively. In the latter case, it has been demonstrated that four molecules of R-diporphyrin assemble into R-box and four molecules of S-diporphyrin assemble into S-box via rigorous homochiral self-sorting process. Efficient excitation energy transfer along these cyclic porphyrin arrays has been revealed by the time-resolved transient absorption and fluorescence measurements. We have also demonstrated that the meso-cinchomeronimide appended Zn(II) porphyrin CIM forms a cyclic trimer, while the corresponding diporphyrins CID exhibit high-fidelity self-sorting assembling to form discrete cyclic trimer, tetramer, and pentamer with large association constants, through perfect discrimination of enantiomeric and conformational differences of the meso-cinchomeronimide substituents.