Leveraging Torsional and Steric Strains: A Pre-macrocyclization Strategy Enables Conformation-Specific Fullerene Binding in m-Cyclophanes

Though the chemistry of resorcinarenes is half a century old, the conformationally-locked resorcinarene crowns are generally constructed using hydrogen bonds or covalent tethers. Often, covalent tethering involves extra post-macrocyclization steps involving upper-rim functionalities. We have leverag...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-10, Vol.62 (41), p.e202305005-e202305005
Main Authors: Kumar, Pawan, Mani Kandan, V B Raja, Balakrishnan, Prabukumar, Antharjanam, P K Sudhadevi, Parthasarathy, Venkatakrishnan
Format: Article
Language:English
Subjects:
Binding
Boats
Conformation
Cyclophane
Fluorescence
Fullerenes
Hydrogen bonding
Hydrogen bonds
Hydrophobicity
Rigidity
Tethering
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Summary:Though the chemistry of resorcinarenes is half a century old, the conformationally-locked resorcinarene crowns are generally constructed using hydrogen bonds or covalent tethers. Often, covalent tethering involves extra post-macrocyclization steps involving upper-rim functionalities. We have leveraged the torsional and steric strains through α-substituents of the lower-rim C-alkyl chains and accomplished conformationally-rigid fluorescent m-cyclophane deep-crowns in a predetermined way. The strategy offers a pre-macrocyclization route conserving upper-rim functionalities, an aspect overlooked in resorcinarene chemistry. X-ray structural and computational analyses unveil the cause for conformational rigidity in m-cyclophanes due to α-branching in C-alkyls (linear vs. α-/β-branched). The conformationally-locked fluorescent deep-crown with a preorganized cavity captures hydrophobic spherical guest C in both solution and solid states specifically, when compared to conformationally-dynamic boats, enabling conformation-specific binding.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202305005