Helical electronic transitions of spiroconjugated molecules. Issue 52 (4th June 2021)

• Record Type: Journal Article
• Authors: Garner, Marc H.; Corminboeuf, Clemence
• Is Part Of: Chemical communications. Volume 57:Issue 52(2021)
• Page Start: 6408
• Page End: 6411
• Publication Date: 2021-06-04
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/d1cc01904j
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : The π–π* transitions of disubstituted spiropentadiene become helical due to mixing of its two perpendicular π-systems. The helicity is symmetry-protected and gives rise to experimentally observable effects, such as optical activity. Abstract : The two π-systems of allene can combine into helical molecular orbitals (MOs), yet the helicity is lost in the π–π* transitions due to excited state mixing. In spiroconjugated molecules the relative orientation of the two π-systems is different and consequently only half the π-MOs become helical. We show that the helicity of the electronic transitions of methyl-substituted spiropentadiene is symmetry protected. As a result, helical π-conjugation can manifest in observable electronic and chiroptical properties.