Enhanced binding strengths of acyclic porphyrin hosts with endohedral metallofullerenes
Enhanced binding strengths of acyclic porphyrin hosts with endohedral metallofullerenes
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DOI：
10.1039/c0sc00569j
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发表时间：
2011-07
期刊：
影响因子：
8.4
通讯作者：
Bruno Grimm;Julia Schornbaum;C. Cardona;J. Paauwe;P. Boyd;D. Guldi
中科院分区：
文献类型：
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作者：
Bruno Grimm;Julia Schornbaum;C. Cardona;J. Paauwe;P. Boyd;D. Guldi
光谱和电化学的互补使用揭示了以双卟啉1和2为主体的杯芳烃支架与一系列富勒烯-C60、Sc3N@C80和Lu3N@C80-作为客体分子的超分子相互作用。重要的是，本工作表明，当C60或面内富勒烯客体被包括在双卟啉主体中时，结合强度发生了显著的变化。这些显著的差异一方面可以通过主客体络合物的计算模型来解释，另一方面可以通过对电子转移化学的系统研究来解释。详细的研究记录了C60包合物的氧化电荷转移(即从双卟啉到富勒烯的电子转移)，而面内金属富勒烯主客体络合物中的还原电荷转移(即从富勒烯到卟啉的电子转移)。
The complementary use of spectroscopy and electrochemistry shed light onto the supramolecular interactions of calixarene scaffold bearing bisporphyrins 1 and 2 as hosts with a series of fullerenes –C60, Sc3N@C80, and Lu3N@C80 – as guest molecules. Importantly, the present work shows a noticeable variation in binding strength when C60 or endohedral fullerene guests are included into the bisporphyrins hosts. These sizeable differences could be clarified by computational models of the host–guest complexes, on the one hand, and a systematic investigation of the electron transfer chemistry, on the other hand. Detailed studies document an oxidative charge transfer (i.e., electron transfer from the bisporphyrin to the fullerene) for the C60 inclusion complexes, while a reductive charge transfer (i.e., electron transfer from the fullerene to porphyrin) is operative in the endohedral metallofullerene host–guest complexes.