6533b7d3fe1ef96bd1260969
RESEARCH PRODUCT
Molecule Isomerism Modulates the Diradical Properties of Stable Singlet Diradicaloids
Eric T. StrandSamantha N. MacmillanMasayoshi NakanoRyohei KishiJustin J. DresslerCarlos J. Gómez-garcíaJuan CasadoAbel Cárdenas ValdiviaMichael M. HaleyJoshua E. BarkerLev N. Zakharovsubject
ChemistryDiradicalBenzothiopheneAromaticityGeneral ChemistryConjugated system010402 general chemistryPhotochemistry01 natural sciencesBiochemistryCatalysis0104 chemical scienceschemistry.chemical_compoundColloid and Surface ChemistryMoleculeSinglet stateCross-conjugationTriplet statedescription
Inclusion of quinoidal cores in conjugated hydrocarbons is a common strategy to modulate the properties of diradicaloids formed by aromaticity recovery within the quinoidal unit. Here we describe an alternative approach of tuning of diradical properties in indenoindenodibenzothiophenes upon anti → syn isomerism of the benzothiophene motif. This alters the relationship of the S atom with the radical center from linear to cross conjugation yet retains the same 2,6-naphtho conjugation pattern of the rearomatized core. We conduct a full comparison between the anti and syn derivatives based on structural, spectroscopic, theoretical, and magnetic measurements, showing that these systems are stable open-shell singlet diradicaloids that only access their triplet state at elevated temperatures.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2019-12-26 | Journal of the American Chemical Society |