Molecule Isomerism Modulates the Diradical Properties of Stable Singlet Diradicaloids
| Autor: | Eric T. Strand, Samantha N. MacMillan, Masayoshi Nakano, Ryohei Kishi, Justin J. Dressler, Carlos J. Gómez-García, Juan Casado, Abel Cárdenas Valdivia, Michael M. Haley, Joshua E. Barker, Lev N. Zakharov |
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| Rok vydání: | 2019 |
| Předmět: |
Chemistry
Diradical Benzothiophene Aromaticity General Chemistry Conjugated system 010402 general chemistry Photochemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Molecule Singlet state Cross-conjugation Triplet state |
| Zdroj: | Journal of the American Chemical Society. 142:1548-1555 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.9b11898 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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