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Flexible C−C Bonds: Reversible Expansion, Contraction, Formation, and Scission of Extremely Elongated Single Bonds
Author(s) -
Shimajiri Takuya,
Suzuki Takanori,
Ishigaki Yusuke
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202010615
Subject(s) - cyclobutane , intramolecular force , chemistry , covalent bond , single bond , bond cleavage , bond order , crystallography , triple bond , bent bond , raman spectroscopy , photodissociation , bond length , photochemistry , double bond , stereochemistry , ring (chemistry) , polymer chemistry , organic chemistry , crystal structure , catalysis , alkyl , physics , optics
Since carbon–carbon (C−C) covalent bonds are rigid and robust, the bond length is, in general, nearly constant and depends only on the bond order and hybrid orbitals. We report herein direct visualization of the reversible expansion and contraction of a C(sp 3 )−C(sp 3 ) single bond by light and heat. This flexibility of a C−C bond was demonstrated by X‐ray analysis and Raman spectroscopy of hexaphenylethane (HPE)‐type hydrocarbons with two spiro‐dibenzocycloheptatriene units, the intramolecular [2+2] photocyclization of which and thermal cleavage of the resulting cyclobutane ring both occur in a single‐crystalline phase. The force constant of the contracted C−C bond is 1.6 times greater than that of the expanded bond. Since formation of the cyclobutane ring and contraction of the C−C bond lower the HOMO level by approximately 1 eV, the oxidative properties of these HPEs with a flexible C−C bond can be deactivated/activated by light/heat.