Revisiting Fluorescent Calixarenes: From Molecular Sensors to Smart Materials

作者：Rajesh Kumar, Amit Kumar Sharma, H.B. Singh, Paolo Suating, Hyeong Seok Kim, Kyoung Sunwoo, Inseob Shim, Bruce C. Gibb, Jong Seung Kim · 发表于：Chemical Reviews · 年份：2019 · DOI：10.1021/acs.chemrev.8b00605 · 被引用次数：541 · 研究领域：Molecular Sensors and Ion Detection、Supramolecular Chemistry and Complexes、Luminescence and Fluorescent Materials

Calix[ n ]arenes ( n = 4, 5, 6, 8) are “chalicelike” phenol-based macrocycles that are among the most fascinating and highly studied scaffolds in supramolecular chemistry. This stems from the functional and tunable diversity at both their upper and lower rims, their preorganized nonpolar cavities and preorganized ion-binding sites, and their well-defined conformations. Conjugation of calixarene scaffolds with various fluorogenic groups has led to the development of smart fluorescent probes that have been utilized as molecular sensors, in bioimaging, for drug and gene delivery, in self-assembly/aggregation, and as smart materials. The fine-tuning and incorporation of different ligating sites in the calix[4]arene scaffold have produced numerous molecular sensors for cations, anions, and biomolecules. Moreover, the aqueous solubility of p -sulfonatocalix[4]arenes has engendered their potential use in drug/gene delivery and enzymatic assays. In addition, because of their strong optical properties, fluorescent calix[4]arenes have been used to develop smart materials, including gels as well as nonlinear optical, organic light-emitting diode, and multiphoton materials. Finally, significant developments in the utility of fluorescent higher calixarenes have been made for bioapplications. This review critically summarizes the recent advances made in all of these different areas.