Selective Potassium Chloride Recognition, Sensing, Extraction, and Transport Using a Chalcogen-Bonding Heteroditopic Receptor.
Selective Potassium Chloride Recognition, Sensing, Extraction, and Transport Using a Chalcogen-Bonding Heteroditopic Receptor.
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DOI：
10.1021/jacs.2c05333
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发表时间：
2022-08-17
影响因子：
15
通讯作者：
Beer, Paul D.
中科院分区：
文献类型：
--
作者：
Docker, Andrew;Marques, Igor;Kuhn, Heike;Zhang, Zongyao;Felix, Vitor;Beer, Paul D.
硫族键（ChB）作为一种强有力的σ-空穴非共价相互作用，在超分子化学中迅速崛起，特别是在分子识别领域的应用。最近的研究表明，ChB供体的强度和效力是显着敏感的局部电子环境，包括氧化还原开关的开/关阴离子结合和传感能力。通过同时结合金属阳离子识别来影响ChB相互作用独特的电子和几何环境敏感性，在本文中，我们提出了第一个氯化钾选择性异位离子对受体。在双碲三唑骨架中，苯并-15-冠-5（B15 C5）与Te中心直接共轭，通过形成共面分子内双-B15 C5 M+（M+ = K+，Rb+，Cs+）夹心配合物和双齿ChB···X-，促进了碱金属卤化物（MX）离子对结合.广泛的定量1H NMR离子对亲和滴定实验，固-液和液-液萃取，和U型管运输研究都证明了前所未有的KCl选择性超过所有其他第1族金属氯化物。它表明，受体的离子对结合的协同性和KCl的选择性的起源来自于由cobound碱金属阳离子诱导的ChB捐助者的电子极化。重要的是，这种开关的大小Te为中心的亲电性，因此阴离子结合亲和力，显示与固有的刘易斯酸性的碱金属阳离子。广泛的计算DFT研究证实了实验碱金属阳离子-阴离子离子对结合卤化物和含氧阴离子的观察。
Chalcogen bonding (ChB) is rapidly rising to prominence in supramolecular chemistry as a powerful sigma (σ)-hole-based noncovalent interaction, especially for applications in the field of molecular recognition. Recent studies have demonstrated ChB donor strength and potency to be remarkably sensitive to local electronic environments, including redox-switchable on/off anion binding and sensing capability. Influencing the unique electronic and geometric environment sensitivity of ChB interactions through simultaneous cobound metal cation recognition, herein, we present the first potassium chloride-selective heteroditopic ion-pair receptor. The direct conjugation of benzo-15-crown-5 ether (B15C5) appendages to Te centers in a bis-tellurotriazole framework facilitates alkali metal halide (MX) ion-pair binding through the formation of a cofacial intramolecular bis-B15C5 M+ (M+ = K+, Rb+, Cs+) sandwich complex and bidentate ChB···X– formation. Extensive quantitative 1H NMR ion-pair affinity titration experiments, solid–liquid and liquid–liquid extraction, and U-tube transport studies all demonstrate unprecedented KCl selectivity over all other group 1 metal chlorides. It is demonstrated that the origin of the receptor’s ion-pair binding cooperativity and KCl selectivity arises from an electronic polarization of the ChB donors induced by the cobound alkali metal cation. Importantly, the magnitude of this switch on Te-centered electrophilicity, and therefore anion-binding affinity, is shown to correlate with the inherent Lewis acidity of the alkali metal cation. Extensive computational DFT investigations corroborated the experimental alkali metal cation–anion ion-pair binding observations for halides and oxoanions.
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影响因子：
16.6
作者：
Barendt, Timothy A.;Docker, Andrew;Marques, Igor;Felix, Vitor;Beer, Paul D.
通讯作者：
Beer, Paul D.
影响因子：
4.9
作者：
Dreger, Alexander;Engelage, Elric;Huber, Stefan M.
通讯作者：
Huber, Stefan M.
影响因子：
15
作者：
Borissov, Arseni;Marques, Igor;Beer, Paul D.
通讯作者：
Beer, Paul D.
影响因子：
4.9
作者：
Docker, Andrew;Martinez Martinez, Antonio J.;Beer, Paul D.
通讯作者：
Beer, Paul D.
影响因子：
16.6
作者：
Bunchuay, Thanthapatra;Docker, Andrew;Beer, Paul D.
通讯作者：
Beer, Paul D.