Influence of Curvature on the Physical Properties and Reactivity of Triplet Corannulene NitreneClick to copy article linkArticle link copied!
- Kelley S. McKissicKelley S. McKissicDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Kelley S. McKissic
- Mrinal ChakrabortyMrinal ChakrabortyDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Mrinal Chakraborty
- Dmitrii GovorovDmitrii GovorovDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Dmitrii Govorov
- Mayukh MajumderMayukh MajumderDepartment of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United StatesMore by Mayukh Majumder
- DeAnte F. JudkinsDeAnte F. JudkinsDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by DeAnte F. Judkins
- Rajkumar MeruguRajkumar MeruguDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Rajkumar Merugu
- H. Dushanee M. SriyarathneH. Dushanee M. SriyarathneDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by H. Dushanee M. Sriyarathne
- Anushree DasAnushree DasDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Anushree Das
- W. Dinindu MendisW. Dinindu MendisDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by W. Dinindu Mendis
- Jan-Simon von GlasenappJan-Simon von GlasenappOtto Diels-Institute for Organic Chemistry, University of Kiel, Otto Hahn Platz 3, Kiel F-24118, GermanyMore by Jan-Simon von Glasenapp
- Rainer HergesRainer HergesOtto Diels-Institute for Organic Chemistry, University of Kiel, Otto Hahn Platz 3, Kiel F-24118, GermanyMore by Rainer Herges
- Christopher M. HadadChristopher M. HadadDepartment of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United StatesMore by Christopher M. Hadad
- James MackJames MackDepartment of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by James Mack
- Manabu AbeManabu AbeDepartment of Chemistry, Hiroshima University, Hiroshima 739-8526, JapanMore by Manabu Abe
- Anna D. Gudmundsdottir*Anna D. Gudmundsdottir*Email: [email protected]Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United StatesMore by Anna D. Gudmundsdottir
Abstract
Although nitrene chemistry is promising for the light-induced modification of organic compounds, the reactivity of large polycyclic aromatic compounds and the effects of their curvature remain unexplored. Irradiation of azidocorannulene (1) in methanol/acetonitrile followed by HCl addition produced diastereomers 5 and 5′. Azirine 2 is apparently trapped by methanol to form diastereomeric acetal derivatives that are hydrolyzed with HCl to yield 5 and 5’. ESR spectroscopy in a glassy matrix at 77 K showed that irradiation of 1 yields corannulene nitrene 31N, which has significant 1,3-biradical character. Irradiation of 1 in a glassy matrix resulted in a new absorption band in the region of 360–440 nm, with λmax at 360 and 410 nm, attributed to 31N, as supported by time-dependent density function theory calculations, which placed the major electronic transitions of 31N at 367 nm (f = 0.0407) and 440 nm (f = 0.0353). Laser flash photolysis of 1 revealed a similar absorption spectrum. Nitrene 31N had a lifetime of only a few hundred nanoseconds and was efficiently quenched by oxygen, because of its 1,3-biradical character. CASPT2(12,11)/6-311G** calculations revealed small energy gap (7.2 kcal/mol) between singlet and triplet configurations, suggesting that 31N is formed by intersystem crossing of 11N to 31N. Spin-density, nucleus-independent chemical shift, and anisotropy of the induced current density calculations verified that 31N is a triplet vinylnitrene with unpaired electrons localized on the C═C–N moiety; decaying by intersystem crossing to 2, which is more stable owing to its aromaticity, as supported by calculations (SA-CASSCF/QD-NEVPT2/CBS).
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