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Title: “Broken-hearted” carbon bowl via electron shuttle reaction: energetics and electron coupling
Unprecedented one-step CC bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene “unzipping” route, we reported a nine-step solution-based approach for preparation of novel planar “open” corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals.  more » « less
Award ID(s):
1955768
NSF-PAR ID:
10225523
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Science
ISSN:
2041-6520
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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    Abstract

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