Toward Stable Superbenzoquinone Diradicaloids

Superbenzoquinone (SBQ) is a quinone derived from a classic polycyclic aromatic hydrocarbon (PAH), hexa‐peri‐hexabenzocoronene (so‐called “superbenzene”), and is a challenging synthetic target. Herein we report the successful synthesis and characterization of its derivatives. We reveal that the high...

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Published inAngewandte Chemie International Edition Vol. 56; no. 18; pp. 5012 - 5016
Main Authors Li, Guangwu, Phan, Hoa, Herng, Tun Seng, Gopalakrishna, Tullimilli Y., Liu, Chunchen, Zeng, Wangdong, Ding, Jun, Wu, Jishan
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 24.04.2017
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Aromatic hydrocarbons
Chemistry
Chemistry, Multidisciplinary
Crystal structure
Derivatives
diradicaloids
dyes/pigments
Ground state
near-infrared dyes
Physical Sciences
Polycyclic aromatic hydrocarbons
Quinones
Science & Technology
Stability
dyes/pigments
HEXAPHENYLBENZENE
QUINOIDAL OLIGOTHIOPHENES
BIRADICALOID CHARACTER
STATE
quinones
diradicaloids
near-infrared dyes
polycyclic aromatic hydrocarbons
HYDROCARBON
SINGLET
MOLECULES
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Summary:Superbenzoquinone (SBQ) is a quinone derived from a classic polycyclic aromatic hydrocarbon (PAH), hexa‐peri‐hexabenzocoronene (so‐called “superbenzene”), and is a challenging synthetic target. Herein we report the successful synthesis and characterization of its derivatives. We reveal that the high reactivity of SBQ is due to its intrinsic open‐shell diradical character. Thus, two kinetically blocked SBQs, SBQ‐Me and SBQ‐Ph, were prepared by different synthetic strategies. 4‐tert‐Butylphenyl‐substituted SBQ‐Ph demonstrated good stability and could be isolated in crystalline form. Both compounds have an open‐shell singlet ground state and show thermally populated paramagnetic activity. Our studies provide effective strategies toward stable quinone‐based diradicaloids. As captivating as a butterfly: Different strategies toward stable superbenzoquinone (SBQ) derivatives were explored, and stable 4‐tert‐phenyl‐substituted SBQ‐Ph was obtained by appropriate kinetic blocking. SBQ‐Ph (see structure) has an open‐shell singlet ground state with moderate diradical character and adopts a butterfly‐like geometry in the single crystal.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201700441