Proximity Effect in Uranyl Coordination of the Cucurbit[6]uril-Bipyridinium Pseudorotaxane Ligand for Promoting Host–Guest Synergistic Chelating,Inorganic Chemistry

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Proximity Effect in Uranyl Coordination of the Cucurbit[6]uril-Bipyridinium Pseudorotaxane Ligand for Promoting Host–Guest Synergistic Chelating
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-07-02 , DOI: 10.1021/acs.inorgchem.1c01177
Fei-Ze Li _{1,

2} , Jun-Shan Geng ₂ , Kong-Qiu Hu ₂ , Ji-Pan Yu ₂ , Ning Liu ₁ , Zhi-Fang Chai _{2,

3} , Lei Mei ₂ , Wei-Qun Shi ₂

Affiliation

In the present work, we proposed regulating uranyl coordination behavior of cucurbituril-bipyridinium pseudorotaxane ligand by utilizing meta-functionalized bipyridinium dicarboxylate guest. A tailored pseudorotaxane precursor involving 1,1′-(hexane-1,6-diyl)bis(3-cyanopyridin-1-ium) bromide (C6BPCN3) and cucurbit[6]uril (CB[6]) has designed and synthesized. Through in situ hydrolysis of the pseudorotaxane ligands and their coordination assembly with uranyl cations, seven new uranyl-rotaxane coordination polymers URCP1–URCP7 have been obtained under hydrothermal conditions in the presence of different anions. It is demonstrated that the variation of carboxylate groups from para- to meta-position greatly affected the coordination behaviors of the meta-functionalized pseudorotaxane linkers, which are enriched from simple guest-only binding to host–guest simultaneous coordination and synergistic chelating. This effective regulation on uranyl coordination of supramolecular pseudorotaxane can be attributed to the proximity effect, which refers to the meta-position carboxyl group being spatially closer to the portal carbonyl group of CB[6]. Moreover, by combining other regulation methods such as introducing competing counterions and modulating solution acidity, the nuclearity of the uranyl center and the coordination patterns of the pseudorotaxane ligand can be diversely tuned, which subsequently exert great influence on the final dimensionality of resultant uranyl compounds. This work presents a large diversity of uranyl-based coordination polyrotaxane compounds with fascinating mechanically interlocked components and, most importantly, provides a feasible approach to adjust and control the metal coordination behavior of the pseudorotaxane ligand that might expand the scope of application of such supramolecular ligands.

中文翻译：

葫芦[6]uril-Bipyridinium Pseudorotaxane配体的铀酰配位的邻近效应促进宿主-客体协同螯合

在目前的工作中，我们提出利用间位官能化联吡啶二羧酸客体来调节葫芦脲-联吡啶鎓假轮烷配体的铀酰配位行为。设计并合成了一种包含 1,1'-(己烷-1,6-二基)双 (3-氰基吡啶-1-鎓) 溴化物 ( C6BPCN3 ) 和葫芦 [6] 脲 (CB[6])的定制假轮烷前体。通过拟轮烷配体的原位水解及其与铀酰阳离子的配位组装，七种新型铀酰-轮烷配位聚合物URCP1-URCP7已在不同阴离子存在下的水热条件下获得。结果表明，羧酸根从对位到间位的变化极大地影响了间位官能化假轮烷接头的配位行为，这些接头从简单的仅客体结合到主客体同时配位和协同螯合丰富。这种对超分子假轮烷铀酰配位的有效调节可归因于邻近效应，即间位羧基在空间上更接近CB的门户羰基[6]。此外，通过结合其他调节方法，例如引入竞争性反离子和调节溶液酸度，铀酰中心的核度和拟轮烷配体的配位模式可以进行多种调整，这对合成的铀酰化合物的最终维数产生很大影响。这项工作提出了大量具有迷人机械互锁成分的铀基配位聚轮烷化合物，最重要的是，提供了一种可行的方法来调节和控制假轮烷配体的金属配位行为，这可能会扩大此类超分子配体的应用范围.

更新日期：2021-07-19

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