Kimura Mutsumi, Nakano Yasuhiro, Adachi Naoya, Tatewaki Yoko, Shirai Hirofusa, Kobayashi Nagao
Department of Functional Polymer Science, Faculty of Textile Science and Technology, Shinshu University, Ueda 386-8567, Japan.
Chemistry. 2009 Mar 2;15(11):2617-24. doi: 10.1002/chem.200801557.
Stable ligation: A series of dendritic porphyrins, such as that depicted in which benzyl ether dendrons were linked to a porphyrin core through 1,2,3-triazole links, was synthesized. Absorption and fluorescence spectra showed a stable axial ligation at the zinc center of the porphyrin core by triazole links in dendritic wedges and indicated that the position of the triazole links strongly affected the stability of the axial ligation within the dendrimer.A series of dendritic porphyrins 7-9 and 12, in which benzyl ether dendrons were linked to a porphyrin core through 1,2,3-triazole links, were synthesized by Cu(I)-catalyzed cycloaddition of azides and alkynes. Absorption and fluorescence spectra showed a stable axial ligation at the zinc center of the porphyrin core by triazole links in dendritic wedges and indicated that the position of the triazole links strongly affected the stability of the axial ligation within the dendrimer. When the porphyrin core was surrounded by aryl ether dendrons having anionic termini and triazole linkers, a significant rate enhancement for photoinduced electron transfer was observed compared with a similar water-soluble dendritic zinc porphyrin lacking triazole linkers. These triazole links constituted a direct pathway within the dendrimer architecture for electron transfer between the zinc porphyrin core and peripheral electron acceptors.
合成了一系列树枝状卟啉，例如其中苄基醚树枝状分子通过1,2,3 - 三唑连接与卟啉核相连的那种。吸收光谱和荧光光谱表明，树枝状楔形结构中的三唑连接在卟啉核的锌中心形成了稳定的轴向配位，并且表明三唑连接的位置强烈影响树枝状大分子内轴向配位的稳定性。通过铜（I）催化的叠氮化物与炔烃的环加成反应，合成了一系列树枝状卟啉7 - 9和12，其中苄基醚树枝状分子通过1,2,3 - 三唑连接与卟啉核相连。吸收光谱和荧光光谱表明，树枝状楔形结构中的三唑连接在卟啉核的锌中心形成了稳定的轴向配位，并且表明三唑连接的位置强烈影响树枝状大分子内轴向配位的稳定性。当卟啉核被具有阴离子末端的芳基醚树枝状分子和三唑连接体包围时，与缺乏三唑连接体的类似水溶性树枝状锌卟啉相比，观察到光诱导电子转移的速率显著提高。这些三唑连接在树枝状大分子结构内构成了锌卟啉核与外围电子受体之间电子转移的直接途径。
