Pyrrole-bridged porphyrin nanorings.
Pyrrole-bridged porphyrin nanorings.
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DOI：
10.1002/chem.201002219
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发表时间：
2010-12
期刊：
影响因子：
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通讯作者：
Jianxin Song;N. Aratani;H. Shinokubo;A. Osuka
中科院分区：
文献类型：
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作者：
Jianxin Song;N. Aratani;H. Shinokubo;A. Osuka
共价连接的环状卟啉阵列主要作为人工光合天线和大的宿主分子进行研究。在这样的阵列中，连接卟啉的各种桥被用来控制整个分子的形状和调节相邻卟啉之间的电子相互作用。其中，经常使用炔属间隔基，因为它们容易并入卟啉阵列中并允许缀合网络的延伸。作为一种不同的方法，我们已经探索了各种环状卟啉阵列的直接介孔-介孔偶联反应的基础上，银促进的耦合和铃木宫浦耦合。4]近年来，我们也探索了芳香杂环桥联的环状卟啉阵列。b-至-B 2，6-吡啶亚基桥联的环状卟啉阵列表现出相对较大的荧光量子产率和较长的荧光寿命，b-至-B 2，5-噻吩亚基桥联的环状卟啉阵列表现出较大的双光子吸收（TPA）截面值，这归因于通过噻吩亚基键的有效电子离域。meso-to-meso 2，2 '-bithiophene-bridged环状卟啉阵列的锌（II）配合物适合于多电荷存储，因此作为分子信息存储系统是令人感兴趣的。作为这些研究的延伸，我们尝试合成meso-to-meso 2，5-吡咯亚基桥联的环状卟啉阵列。环卟啉纳米环中的吡咯桥由于其富电子性质、有效的共轭和可能的氢键贡献能力而非常有吸引力。此外，如方案1中的环状卟啉三聚体所示，我们可以考虑一种形式的六卟啉-
Covalently linked, cyclic porphyrin arrays have been explored mainly as artificial photosynthetic antennae and large host molecules. In such arrays, a variety of bridges that connect porphyrins have been employed to control the overall molecular shape and to tune the electronic interaction between neighboring porphyrins. Among these, acetylenic spacers have been often used, because these are easy to incorporate into porphyrin arrays and allow for elongation of conjugation networks. As a different approach, we have explored various cyclic porphyrin arrays by direct meso–meso coupling reactions on the basis of Ag-promoted coupling and Suzuki–Miyaura coupling. 4] In recent years, we have also explored aromatic heterocycle-bridged cyclic porphyrin arrays. The b-to-b 2,6-pyridylene-bridged cyclic porphyrin arrays exhibit relatively large fluorescence quantum yields and long fluorescent lifetimes, and b-to-b 2,5thienylene-bridged cyclic porphyrin arrays exhibit large twophoton absorption (TPA) cross-section values, owing to effective electronic delocalization through the thienylene linkages. Zinc(II) complexes of meso-to-meso 2,2’-bithiophene-bridged cyclic porphyrin arrays are suitable for multicharge storage and hence are of interest as molecular information storage systems. As an extension of these studies, we attempted to synthesize meso-to-meso 2,5-pyrrolylene-bridged cyclic porphyrin arrays. A pyrrole bridge in cyclic porphyrin nanorings is quite attractive in view of its electron-rich properties, effective conjugation, and possible hydrogen-bonding donating ability. In addition, as indicated for the cyclic porphyrin trimer in Scheme 1, we can consider a formal hexaphyrin-