Please use this identifier to cite or link to this item: https://doi.org/10.1021/acs.joc.9b02796
Title: Sulfur-Doped (Dibenzo)heptazethrene and (Dibenzo)octazethrene Diradicaloids
Authors: C. H. E. Chow
PHAN VAN HOA 
ZHANG XIAOJIE 
Wu Jishan 
Issue Date: 12-Nov-2019
Publisher: ACS
Citation: C. H. E. Chow, PHAN VAN HOA, ZHANG XIAOJIE, Wu Jishan (2019-11-12). Sulfur-Doped (Dibenzo)heptazethrene and (Dibenzo)octazethrene Diradicaloids. Journal of Organic Chemistry 85 : 234-240. ScholarBank@NUS Repository. https://doi.org/10.1021/acs.joc.9b02796
Abstract: We report the synthesis and characterization of sulfur-doped dibenzoheptazethrene (DBHZ-2S) and dibenzooctazethrene (DBOZ-2S) dications. Their neutral precursors 9a/9b were synthesized by acid-mediated intramolecular cyclization reaction of sulfoxides and the dications were prepared by treating 9a/9b with NOSbF6 or AgSbF6, respectively. Both dications displayed open-shell singlet ground state with a moderate diradical character (y0 = 0.44 for DBHZ-2S and 0.66 for DBOZ-2S) and a small singlet−triplet energy gap (ΔES‑T = −3.9 kcal/mol for DBHZ-2S and −3.2 kcal/mol for DBOZ-2S). The open-shell singlet diradical nature of DBHZ-2S and DBOZ-2S were supported by electronic absorption spectroscopy, electron spin resonance spectroscopy, variable-temperature NMR studies, together with spin-unrestricted density functional theory calculations. However, synthesis and isolation of the sulfur-doped heptazethrene (HZ-2S) and octazethrene (OZ-2S) dications upon chemical oxidation of their corresponding neutral precursors 5a/5b were not successful owing to their high reactivity.
Source Title: Journal of Organic Chemistry
URI: https://scholarbank.nus.edu.sg/handle/10635/167849
ISSN: 0022-3263
1520-6904
DOI: 10.1021/acs.joc.9b02796
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