Rather Ishfaq Ahmad, Danjou Pierre-Edouard, Ali Rashid
Organic and Supramolecular Functional Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, Jamia Nagar, Okhla, New Delhi, 110025, India.
Unité de Chimie Environnementale et Interactions Sur le Vivant, UR 4492, Université du Littoral Côte d'Opale, 145 Avenue Maurice Schumann, MREI 1, 59140, Dunkirk, France.
Top Curr Chem (Cham). 2023 Jan 6;381(1):7. doi: 10.1007/s41061-022-00419-0.
The incorporation of aryl substituents at the meso-positions of calix[4]pyrrole (C4P) scaffolds produces aryl-extended (AE) and super-aryl-extended (SAE) calix[4]pyrroles. The cone conformation of the all-α isomers of "multi-wall" AE-C4Ps and SAE-C4Ps displays deep aromatic clefts or cavities. In particular, "four-wall" receptors feature an aromatic polar cavity closed at one end with four convergent pyrrole rings and fully open at the opposite end. This makes AE- and SAE-C4P scaffolds effective receptors for the molecular recognition of negatively charged ions and neutral guest molecules with donor-acceptor and hydrogen bonding motifs. In addition, adequately functionalized all-α isomers of multi wall AE- and SAE-C4P scaffolds self-assemble into uni-molecular and supra-molecular aggregates displaying capsular and cage-like structures. The self-assembly process requires the presence of template ions or molecules that lock the C4P cone conformation and complementing the inner polar functions and volumes of their cavities. We envisioned performing an in-depth revision of AE- and SAE-C4P scaffolds owing to their importance in different domains such as supramolecular chemistry, biology, material sciences and pharmaceutical chemistry. Herewith, besides the synthetic details on the elaboration of their structures, we also draw attention to their diverse applications. The organization of this review is mainly based on the number of "walls" present in the AE-C4P derivatives and their structural modifications. The sections are further divided based on the C4P functions and applications. The authors are convinced that this review will be of interest to researchers working in the general area of supramolecular chemistry as well as those involved in the study of the binding properties and applications of C4P derivatives.
在杯[4]吡咯（C4P）支架的中位引入芳基取代基可生成芳基扩展（AE）和超芳基扩展（SAE）杯[4]吡咯。“多壁”AE-C4P和SAE-C4P的全α异构体的锥形构象显示出深的芳香族裂缝或空腔。特别是，“四壁”受体具有一个芳香族极性空腔，一端由四个汇聚的吡咯环封闭，另一端完全开放。这使得AE-和SAE-C4P支架成为用于分子识别带负电荷离子以及具有供体-受体和氢键基序的中性客体分子的有效受体。此外，多壁AE-和SAE-C4P支架的充分官能化的全α异构体自组装成具有胶囊状和笼状结构的单分子和超分子聚集体。自组装过程需要存在模板离子或分子，以锁定C4P的锥形构象并补充其空腔的内部极性功能和体积。由于AE-和SAE-C4P支架在超分子化学、生物学、材料科学和药物化学等不同领域的重要性，我们设想对其进行深入综述。在此，除了阐述其结构的合成细节外，我们还提请注意它们的各种应用。本综述的组织主要基于AE-C4P衍生物中存在的“壁”的数量及其结构修饰。各部分进一步根据C4P的功能和应用进行划分。作者相信，本综述将引起超分子化学一般领域的研究人员以及参与C4P衍生物结合特性和应用研究的人员的兴趣。
