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Shape-Shifting Tetralactam Macrocycles: Protonation-Activated Convergent Hydrogen Bonding.

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Τίτλος: Shape-Shifting Tetralactam Macrocycles: Protonation-Activated Convergent Hydrogen Bonding.
Συγγραφείς: Liu D; Department of Chemistry, University of South Florida, Tampa, FL, USA., Victoria A; Department of Chemistry, University of South Florida, Tampa, FL, USA., Mariscal A; Department of Chemistry, University of South Florida, Tampa, FL, USA., Conces J; Department of Chemistry, University of South Florida, Tampa, FL, USA., Mampilly S; Department of Chemistry, University of South Florida, Tampa, FL, USA., Cui Y; Department of Chemistry, University of South Florida, Tampa, FL, USA., Wojtas L; Department of Chemistry, University of South Florida, Tampa, FL, USA., Cai J; Department of Chemistry, University of South Florida, Tampa, FL, USA., Liu W; Department of Chemistry, University of South Florida, Tampa, FL, USA.
Πηγή: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2026 Jan 23; Vol. 32 (4), pp. e03496. Date of Electronic Publication: 2025 Dec 15.
Τύπος έκδοσης: Journal Article
Γλώσσα: English
Στοιχεία περιοδικού: Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 9513783 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3765 (Electronic) Linking ISSN: 09476539 NLM ISO Abbreviation: Chemistry Subsets: MEDLINE; PubMed not MEDLINE
Imprint Name(s): Original Publication: Weinheim, Germany : Wiley-VCH
Περίληψη: Integrating high binding affinity with dynamic, stimuli-responsive control represents a pivotal objective in synthetic receptor design, with far-reaching implications for sensing, separation, and molecular machinery. We report a class of shape-shifting tetralactam macrocycles featuring embedded 2,4-pyridinedicarboxamide units as switching elements. In their neutral state, these macrocycles adopt divergent hydrogen-bonding conformations that exhibit low substrate affinity. Upon protonation, a reversible conformational reorganization occurs, reorienting four amide N-H groups toward the cavity to form a convergent, high-affinity hydrogen-bonding pocket. Conformational switching was confirmed by X-ray crystallography and solution-phase NMR. Upon protonation, these macrocycles exhibit >10⁵-fold binding enhancement, achieving association constants up to 135,000 M-1 for the polyhalide anion BrIBr-. Computational analysis reveals that this dramatic increase arises from synergistic hydrogen bonding, electrostatic attraction, and van der Waals interactions. These findings establish a robust strategy for designing adaptive hydrogen-bonding receptors that combine dynamic switching with high substrate affinity and selectivity. The ability to toggle between low- and high-affinity states without sacrificing structural integrity sets the stage for expanding the scope of smart molecular systems with tunable recognition properties.
(© 2025 Wiley‐VCH GmbH.)
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Grant Information: CHE-2337419 National Science Foundation
Contributed Indexing: Keywords: anion recognition; hydrogen bonds; macrocycle; molecular switches
Entry Date(s): Date Created: 20251215 Latest Revision: 20260127
Update Code: 20260130
DOI: 10.1002/chem.202503496
PMID: 41395864
Βάση Δεδομένων: MEDLINE
Περιγραφή
ISSN:1521-3765
DOI:10.1002/chem.202503496