Conformational effects on iodide binding: a comparative study of flexible and rigid carbazole macrocyclic analogs
Year: 2025
Type: article
Abstract: To our knowledge, this work represents one of the earliest comparative studies on the anion-binding behaviors of carbazole-based structural analogs, demonstrating that a flexible macrocycle markedly improves iodide binding affinity via an induced-fit mechanism. The flexible analog PBG exhibits a 22.78-fold higher fluorescence quenching efficiency upon iodide binding compared to the rigid WDG ( K PBG / K WDG = 22.78), demonstrating its potential as a highly sensitive optical probe and offering a novel strategy for engineering dynamic supramolecular receptors. Two carbazole-based macrocyclic probes, PBG (flexible benzene ring) and WDG (rigid fluorene backbone), were synthesized via Friedel–Crafts reactions. Their iodide (I − ) recognition properties were systematically explored using 1 H NMR, UV–vis absorption, and fluorescence spectroscopy. Quantitative analysis via the Benesi–Hildebrand equation and nonlinear fitting demonstrated that flexible PBG achieves superior I − binding ( K PBG = 1.387 × 10 5 M −1 ) through induced-fit conformational adjustments, whereas rigid WDG ( K WDG = 6.089 × 10 3 M −1 ) is constrained by preorganized cavity geometry, adhering to a conformational selection mechanism. This work elucidates the synergistic interplay between conformational dynamics and localized structural adaptations governing anion recognition. The findings advance the rational design of tunable, high-affinity anion receptors and deepen the understanding of conformational regulation in supramolecular systems.
DOI: 10.3762/bjoc.21.181
Authors: Guang-Wei Zhang, Yong Zhang, Le Shi, Chuang Gao, Hong-Yu Li, Lei Xue
Institution: Nanjing University of Posts and Telecommunications
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Awards: G4705143484, G5789189689, G8317533372
OpenAlex ID: W4415803864