All-hydrocarbon, all-conjugated cycloparaphenylene-polycyclic aromatic hydrocarbon host–guest complexes stabilized by CH–π interactions
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Polycyclic aromatic hydrocarbons (PAHs) are promising nanocarbon materials with diverse optoelectronic properties, yet they also pose concerning environmental and health risks. Despite the ubiquity of PAHs in the environment (crude oil, emissions, and biomass), most supermolecules rely on heteroatoms for stability. We discovered and characterized a family of all-hydrocarbon, all-π-conjugated [n]cycloparaphenylene-PAH host–guest complexes. We built a theoretical framework to rapidly select these complexes and predict their stabilities, driven exclusively by CH–π interactions. More than a dozen complexes were confirmed experimentally and assembled directly from commercially available compounds. This motif offers a versatile way to combine the advantageous properties of organic semiconductors with the rich dynamic, stereochemical, stimulus-responsive, and stress-dissipative behavior of host–guest complexes, while creating new opportunities for bespoke PAH separation or remediation materials.
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All-hydrocarbon, all-conjugated cycloparaphenylene-polycyclic aromatic hydrocarbon host–guest complexes stabilized by CH–π interactions
)
Abstract
Polycyclic aromatic hydrocarbons (PAHs) are promising nanocarbon materials with diverse optoelectronic properties, yet they also pose concerning environmental and health risks. Despite the ubiquity of PAHs in the environment (crude oil, emissions, and biomass), most supermolecules rely on heteroatoms for stability. We discovered and characterized a family of all-hydrocarbon, all-π-conjugated [n]cycloparaphenylene-PAH host–guest complexes. We built a theoretical framework to rapidly select these complexes and predict their stabilities, driven exclusively by CH–π interactions. More than a dozen complexes were confirmed experimentally and assembled directly from commercially available compounds. This motif offers a versatile way to combine the advantageous properties of organic semiconductors with the rich dynamic, stereochemical, stimulus-responsive, and stress-dissipative behavior of host–guest complexes, while creating new opportunities for bespoke PAH separation or remediation materials.
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Acknowledgements
The authors acknowledge Dr. Bimala Lama, the Department of Chemistry, and the Raman Microspectroscopy Laboratory at the University of Colorado Boulder for the use of NMR, UV–Vis–NIR, FL, and Raman spectroscopy instrumentation. The authors also acknowledge the Materials and Molecular Analysis Center at Colorado State University for the use of MALDI-TOF-MS instrumentation. This study was partly supported by the American Chemical Society Petroleum Research Fund Doctoral New Investigator grant (No. 59067-DNI7). Further support was provided by the College of Engineering and Applied Science at the University of Colorado Boulder. This work utilized resources from the University of Colorado Boulder Research Computing Group, which is supported by the National Science Foundation (awards ACI-1532235 and ACI-1532236), the University of Colorado Boulder, and Colorado State University.
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