Fullerene-Functionalized Halogen-Bonding Heteroditopic Hosts for Ion-Pair Recognition.
Fullerene-Functionalized Halogen-Bonding Heteroditopic Hosts for Ion-Pair Recognition.
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DOI：
10.1021/jacs.3c07774
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发表时间：
2023-12-20
影响因子：
15
通讯作者：
Beer, Paul D.
中科院分区：
文献类型：
--
作者：
Bak, Krzysztof M.;Marques, Igor;Kuhn, Heike;Christensen, Kirsten E.;Felix, Vitor;Beer, Paul D.
尽管它们的疏水表面具有局部π-孔和刚性明确的结构，为预组织结合基序提供了支架，但富勒烯仍然未被开发为用于识别阴离子的潜在超分子主体平台。在此，我们提出了第一个例子的合理设计，合成，和独特的识别性能的新的富勒烯功能化卤素键合（XB）异源离子对受体含有阳离子和阴离子的结合域空间分离的C60。富勒烯空间分离的XB捐助者和冠醚络合的钾阳离子导致在一个罕见的例子，人工受体含有两个阴离子结合位点与硬和软卤化物相反的偏好。重要的是，将C60基序掺入异位受体结构中对卤化物结合选择性具有显著影响，其在K+阳离子结合后进一步放大。钾阳离子络合的富勒烯受体表现出对软可极化碘离子的增强的选择性，这是由C60支架预组织有效的XB-基结合域，阴离子-π相互作用和富勒烯部分的特殊极化性所辅助的，如DFT计算所证明的。这些观察结果有助于突出富勒烯表面的独特性能，近端带电客体结合与潜在的应用在选择性分子传感器的建设和调制的太阳能电池器件的性能。
Despite their hydrophobic surfaces with localized π-holes and rigid well-defined architectures providing a scaffold for preorganizing binding motifs, fullerenes remain unexplored as potential supramolecular host platforms for the recognition of anions. Herein, we present the first example of the rational design, synthesis, and unique recognition properties of novel fullerene-functionalized halogen-bonding (XB) heteroditopic ion-pair receptors containing cation and anion binding domains spatially separated by C60. Fullerene spatial separation of the XB donors and the crown ether complexed potassium cation resulted in a rare example of an artificial receptor containing two anion binding sites with opposing preferences for hard and soft halides. Importantly, the incorporation of the C60 motif into the heteroditopic receptor structure has a significant effect on the halide binding selectivity, which is further amplified upon K+ cation binding. The potassium cation complexed fullerene-based receptors exhibit enhanced selectivity for the soft polarizable iodide ion which is assisted by the C60 scaffold preorganizing the potent XB-based binding domains, anion−π interactions, and the exceptional polarizability of the fullerene moiety, as evidenced from DFT calculations. These observations serve to highlight the unique properties of fullerene surfaces for proximal charged guest binding with potential applications in construction of selective molecular sensors and modulating the properties of solar cell devices.
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影响因子：
15
作者：
Chen, Qiang;Thompson, Amber L.;Christensen, Kirsten E.;Horton, Peter N.;Coles, Simon J.;Anderson, Harry L.
通讯作者：
Anderson, Harry L.
DOI：
10.1002/anie.202101732
发表时间：
2021-07-05
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Chen D;Liu S;Chen D;Liu J;Wu J;Wang H;Su Y;Kwak G;Zuo X;Rao D;Cui H;Shu C;Suk JS
通讯作者：
Suk JS
影响因子：
15
作者：
Docker, Andrew;Marques, Igor;Kuhn, Heike;Zhang, Zongyao;Felix, Vitor;Beer, Paul D.
通讯作者：
Beer, Paul D.
影响因子：
16.6
作者：
Grauwels, Glenn;Valkenier, Hennie;Bartik, Kristin
通讯作者：
Bartik, Kristin
影响因子：
15
作者：
Barendt, Timothy A.;Myers, William K.;Beer, Paul D.
通讯作者：
Beer, Paul D.