Orthogonal actuation of a supramolecular double-porphyrin tweezer.
Orthogonal actuation of a supramolecular double-porphyrin tweezer.
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超分子双卟啉镊子的正交驱动
DOI：
10.1021/jo101169f
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
S. K. Samanta
中科院分区：
文献类型：
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作者：
M. Schmittel;S. K. Samanta
超分子三组分双卟啉镊子 (PT) 采用 HETTAP 方法形成杂配复合物来定量制备。将客体分子（例如 DABCO 或吡嗪）插入 PT 的偶联卟啉空腔中会导致双卟啉镊子功能的启动。 1 H NMR、VT NMR 和 UV-vis 滴定的证据表明 DABCO 分子在中心卟啉处快速缔合/解离。将 DABCO 和吡嗪的等摩尔混合物添加到 PT 中后，独家提供了动态五组分自组装结构。 1 H NMR 和 Kassoc 值验证了异质负载 PT-(DABCO)(py) 系统与两种同质负载系统 PT-(DABCO)2 和 PT-(py)2 相比具有更高的稳定性。 PT-(DABCO)(py)的较高稳定性似乎是电荷从DABCO穿过卟啉平面转移到吡嗪的空π*轨道的结果。
A supramolecular three-component double-porphyrin tweezer (PT) is prepared quantitatively using heteroleptic complex formation along the HETTAP methodology. Insertion of guest molecules, such as DABCO or pyrazine, into the coupled porphyrin cavities ofPTleads to an actuation of the double-porphyrin tweezer function. Evidence from1H NMR, VT NMR, and UV−vis titration suggests a rapid association/dissociation of the DABCO molecules at the central porphyrin. Upon addition of an equimolar mixture of DABCO and pyrazine toPT, a dynamic five-component self-assembled structure was furnished exclusively.1H NMR andKassocvalues validate the greater stability of the heteroloadedPT-(DABCO)(py) system in comparison to the two homoloaded systems,PT-(DABCO)2andPT-(py)2. The higher stability ofPT-(DABCO)(py) seems to be the result of charge transfer from DABCO to the vacant π* orbital of pyrazine across the porphyrin plane.