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- Title
Mono‐reduced Corannulene: To Couple and Not to Couple in One Crystal.
- Authors
Rogachev, Andrey Yu.; Alkan, Melisa; Li, Jingbai; Liu, Shuyang; Spisak, Sarah N.; Filatov, Alexander S.; Petrukhina, Marina A.
- Abstract
One‐electron reduction of corannulene, C20H10, with Li metal in diglyme resulted in crystallization of [{Li+(diglyme)2}4(C20H10.−)2(C20H10‐C20H10)2−] (1), as revealed by single‐crystal X‐ray diffraction. This hybrid product contains two corannulene monoanion‐radicals along with a dianionic dimer, crystallized with four Li+ ions wrapped by diglyme molecules. The dimeric (C20H10‐C20H10)2− anion provides the first crystallographically confirmed example of spontaneous radical dimerization for C20H10.−. The C−C bond length between the two C20H10.− bowls of 1.588(5) Å is consistent with the single σ‐bond character of the linker. The trans‐disposition of two bowls in the centrosymmetric (C20H10‐C20H10)2− dimer is observed with the torsion angle around the central C−C bond of 180°. Comprehensive theoretical analysis of formation/decomposition processes of the dimeric dianion has been carried out in order to evaluate the nature of bonding and energetics of the C20H10.− coupling. It is found that such σ‐bonded dimers are thermodynamically unstable due to large preparation energy and repulsive Pauli component of the bonding, but kinetically persistent due to a high energy barrier provided by the existing spin‐crossing point.
- Subjects
CORANNULENE; RADICAL anions; DIHEDRAL angles; ACTIVATION energy; CHEMICAL bond lengths; MOLECULAR structure
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 62, p14140
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201902992