Single and Multiple Binding of β-Cyclodextrin and Polymeric β-Cyclodextrins to Luminescent Ruthenium(II) α-Diimine Complexes

Single and Multiple Binding of β-Cyclodextrin and Polymeric β-Cyclodextrins to Luminescent Ruthenium(II) α-Diimine Complexes
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DOI:
10.1021/jp0116149
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发表时间:
2002
影响因子:
2.9
通讯作者:
Wenying Xu;A. Jain;B. A. Betts;†. A. J. N. Demas;B. DeGraff
Wenying Xu;A. Jain;B. A. Betts;†. A. J. N. Demas;B. DeGraff
中科院分区:
化学3区
文献类型:
--
作者:
Wenying Xu;A. Jain;B. A. Betts;†. A. J. N. Demas;B. DeGraff

文献摘要

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对具有多个结合位点的钌配合物与单体和聚合 β-环糊精之间的结合相互作用进行了全面研究。发现了涉及单个和多个结合排列的多种不同的结合模式。结合很大程度上取决于客体和主体的几何形状以及疏水性效应。为了利用客体的多个附着点的几何形状,环糊精单元存在最佳间距。在 CD 结合时,复合物免受氧猝灭。与游离复合物相比,即使只有一小部分复合物表面受到保护,淬火也可减少 3 至 10 倍以上。大大增强的屏蔽可归因于激励位于受保护区域内。对于聚合物主体,相关的连接体也可以帮助屏蔽。讨论了这些结果对聚合物支持的猝灭氧传感器的影响。
A comprehensive study of the binding interactions between ruthenium complexes with multiple binding sites and monomeric and polymeric β-cyclodextrins is presented. A variety of different binding modes involving single and multiple binding arrangements are found. Binding is critically dependent on the geometry of the guest and host and hydrophobicity effects. There is an optimal spacing of the cyclodextrin units in order to exploit the geometry of the multiple attachment points of the guest. On CD binding, the complexes are shielded from oxygen quenching. Quenching can be reduced by from 3 to greater than 10 times compared to the free complex even though only a small portion of the surface of the complex is protected. The greatly enhanced shielding can be attributed to the excitation being localized in the protected region. With the polymeric hosts, the associated linker can also assist in shielding. Implications of these results to polymer supported quenchometric oxygen sensors are discussed.