Late-Stage Modification of Electronic Properties of Antiaromatic and Diradicaloid Indeno[1,2‑b]fluorene Analogues via Sulfur Oxidation

The ability to alter optoelectronic and magnetic properties of molecules at a late stage in their preparation is in general a nontrivial feat. Here, we report the late-stage oxidation of benzothiophene-fused indacenes and dicyclopentanaphthalenes to their corresponding sulfone derivatives. We find t...

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Bibliographic Details
Published in:Journal of organic chemistry 2020-08, Vol.85 (16), p.10846-10857
Main Authors: Dressler, Justin J, Barker, Joshua E, Karas, Lucas J, Hashimoto, Hannah E, Kishi, Ryohei, Zakharov, Lev N, MacMillan, Samantha N, Gomez-Garcia, Carlos J, Nakano, Masayoshi, Wu, Judy I, Haley, Michael M
Format: Article
Language:English
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Summary:The ability to alter optoelectronic and magnetic properties of molecules at a late stage in their preparation is in general a nontrivial feat. Here, we report the late-stage oxidation of benzothiophene-fused indacenes and dicyclopentanaphthalenes to their corresponding sulfone derivatives. We find that while such modifications increase the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap to a small degree, other properties such as HOMO and LUMO energy levels, molecule paratropicity, and singlet-triplet energy gaps are influenced to a greater degree. The most surprising finding is a change of the bond alternation pattern within the s-indacene core of the sulfones. Computations corroborate the experimental findings and offer plausible explanations for these changes in molecular properties.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.0c01387