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Smart Hydrogen Atoms in Heterocyclic Cations of 1,2,4-Triazolium-Type Poly(ionic liquid)s
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2022-12-05 , DOI: 10.1021/acs.accounts.2c00430
Si-Hua Liu 1 , Hong Wang 2 , Jian-Ke Sun 1 , Markus Antonietti 3 , Jiayin Yuan 4
Affiliation  

Discovering and constructing molecular functionality platforms for materials chemistry innovation has been a persistent target in the fields of chemistry, materials, and engineering. Around this task, basic scientific questions can be asked, novel functional materials can be synthesized, and efficient system functionality can be established. Poly(ionic liquid)s (PILs) have attracted growing interest far beyond polymer science and are now considered an interdisciplinary crossing point between multiple research areas due to their designable chemical structure, intriguing physicochemical properties, and broad and diverse applications. Recently, we discovered that 1,2,4-triazolium-type PILs show enhanced performance profiles, which are due to stronger and more abundant supramolecular interactions ranging from hydrogen bonding to metal coordination, when compared with structurally similar imidazolium counterparts. This phenomenon in our view can be related to the smart hydrogen atoms (SHAs), that is, any proton that binds to the carbon in the N-heterocyclic cations of 1,2,4-triazolium-type PILs. The replacement of one carbon by an electron-withdrawing nitrogen atom in the broadly studied heterocyclic imidazolium ring will further polarize the C–H bond (especially for C5–H) of the resultant 1,2,4-triazolium cation and establish new chemical tools for materials design. For instance, the H-bond-donating strength of the SHA, as well as its Bro̷nsted acidity, is increased. Furthermore, polycarbene complexes can be readily formed even in the presence of weak or medium bases, which is by contrast rather challenging for imidazolium-type PILs. The combination of SHAs with the intrinsic features of heterocyclic cation-functionalized PILs (e.g., N-coordination capability and polymeric multibinding effects) enables new phenomena and therefore innovative materials applications.

中文翻译:

1,2,4-三唑鎓型聚离子液体杂环阳离子中的智能氢原子

发现和构建材料化学创新的分子功能平台一直是化学、材料和工程领域的一个持久目标。围绕这一任务,可以提出基本的科学问题,合成新的功能材料,建立高效的系统功能。聚(离子液体)(PIL)吸引了越来越多的兴趣,远远超出了高分子科学,并且由于其可设计的化学结构、有趣的物理化学性质以及广泛多样的应用,现在被认为是多个研究领域之间的跨学科交叉点。最近,我们发现 1,2,4-三唑鎓型 PIL 表现出增强的性能特征,这是由于从氢键到金属配位的超分子相互作用更强和更丰富,与结构相似的咪唑鎓对应物相比。在我们看来,这种现象可能与智能氢原子 (SHA) 有关,即与 1,2,4-三唑鎓型 PIL 的 N-杂环阳离子中的碳结合的任何质子。在广泛研究的杂环咪唑环中用吸电子氮原子取代一个碳将进一步极化所得 1,2,4-三唑阳离子的 C-H 键(尤其是 C5-H)并建立新的化学工具用于材料设计。例如,SHA 的氢键供给强度及其 Bro̷nsted 酸度增加。此外,即使在弱碱或中碱存在的情况下,也可以很容易地形成聚卡宾络合物,相比之下,这对于咪唑鎓型 PIL 来说相当具有挑战性。
更新日期:2022-12-05
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