Ag(I)-linked Bis-calix[4]pyrrole Molecular Capsule and its Selective Recognition of Fluoride Anion

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2024-12-17 DOI:10.1039/d4qo02177k

Xiaolong Chen, Zhiye Zheng, Shunfeng Peng, Ying Guo, Ying Gao, Chenxing Guo, Jonathan L. Sessler, Hong-Yu Wang

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引用次数: 0

Abstract

A well-defined “four-wall” capsule (3) was constructed based on the coordination-driven self-assembly of a tetratopic pyridine-functionalized calix[4]pyrrole cavitand with four stabilizing pyridine···Ag+···pyridine coordination bonds in N,N-dimethylformamide (DMF). Capsule was 3 characterized by means of various techniques, including 1H nuclear magnetic resonance (NMR) spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI-MS), and single crystal X-ray diffraction analyses. The tetra-α-meso-pyridyl extended calix[4]pyrrole ligand 2 and the corresponding dimeric capsule 3 were found to recognize selectively the fluoride anion over other halide anions (chloride, bromide, and iodide anions) in DMF. Cavitand 2 was found to bind and release Ag+ via a fast equilibrium exchange process on the NMR timescale, whereas the ﬂuoride binding of both 2 and capsule 3 proved slow on the NMR timescale. The transformation among multiple molecular states, viz. monomeric form 2, capsule 3, and their corresponding fluoride-bound complexes F−⊂2 and 2F−⊂3, could be modulated by the addition of silver, fluoride, and chloride ions.

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Ag(I)-linked Bis-calix[4]pyrrole 分子胶囊及其对氟阴离子的选择性识别

在 N,N-二甲基甲酰胺（DMF）中，四位吡啶功能化的钙并[4]吡咯空穴带与四个稳定的吡啶--Ag+--吡啶配位键在配位驱动下自组装，从而构建了一个定义明确的 "四壁 "胶囊（3）。通过各种技术，包括 1H 核磁共振（NMR）光谱、扩散有序 NMR 光谱（DOSY）、电喷雾离子化质谱（ESI-MS）和单晶 X 射线衍射分析，对胶囊进行了表征。研究发现，在 DMF 中，四-α-甲磺酰基吡啶基扩展钙[4]吡咯配体 2 和相应的二聚胶囊 3 能选择性地识别氟阴离子，而不是其他卤化物阴离子（氯、溴和碘阴离子）。在核磁共振时间尺度上，Cavitand 2 通过快速的平衡交换过程结合和释放 Ag+，而在核磁共振时间尺度上，2 和胶囊 3 的氟化物结合都很缓慢。加入银离子、氟离子和氯离子可以调节多种分子状态之间的转变，即单体形式2、胶囊3及其相应的氟化物结合复合物F-⊂2和2F-⊂3。

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来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.