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Tuning strained alkyne reactivity via organic synthesis has evolved into a burgeoning field of study largely focused on cyclooctyne, wherein physical organic chemistry helps guide rational molecular design to produce molecules with intriguing properties. Concurrent research in the field of carbon nanomaterials has produced new types of strained alkyne macrocycles, such as cycloparaphenyleneacetylenes, that possess uniquely curved aromatic π systems but hover on the edge of stability. In 2018, we introduced a strained alkyne scaffold that marries the synthetic accessibility and stability of cyclooctyne with the curved π system of carbon nanomaterials. These molecules are strained alkyne-containing cycloparaphenylenes (or [n+1]CPPs), which have been shown to possess size-dependent reactivity as well as the classic characteristics of the unfunctionalized parent CPP, such as a tunable HOMO–LUMO gap and bright fluorescence for large sizes. Herein, we elaborate further on this scaffold, introducing two modifications to the original design and fully characterizing the kinetics of the strain-promoted azide–alkyne cycloaddition (SPAAC) for each [n+1]CPP with a model azide. Additionally, we explain how electronic (the incorporation of fluorine atoms) and strain (a meta linkage which heightens local strain at the alkyne) modulations affect SPAAC reactivity via the distortion–interaction computational model. Altogether, these results indicate that through a modular synthesis and rational chemical design, we have developed a new family of tunable and inherently fluorescent strained alkyne carbon nanomaterials.
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Strain‐Promoted Reactivity of Alkyne‐Containing Cycloparaphenylenes
Abstract A new class of macrocyclic angle‐strained alkynes whose size and reactivity can be precisely tuned by modular organic synthesis is disclosed. Detailed analysis of the size‐dependent structural and electronic properties provides evidence for considerable distortion of the alkyne units incorporated into the cycloparaphenylene (CPP)‐derived macrocycles. The remarkable increase of the alkyne reactivity with decreasing macrocycle size in [2+2]cycloaddition–retrocyclization was investigated by joint experimental and theoretical studies and the thermodynamic and kinetic parameters that govern this reaction were unraveled. Additionally, even the largest, least strained macrocycle in this series was found to undergo strain‐promoted azide–alkyne cycloaddition (SPAAC) efficiently under mild conditions, thereby paving the way to the application of alkyne‐containing CPPs as fluorescent “clickable” macrocyclic architectures.
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- PAR ID:
- 10079504
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 57
- Issue:
- 50
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 16348-16353
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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