Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure
Park, Kyu Hyung
Herng, Tun Seng
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AbstractThe fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.
CitationOctazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure 2016 The Journal of Organic Chemistry
SponsorsJ. W. acknowledges the financial support from the MOE Tier 3 Programme (MOE2014-T3-1-004), Tier 2 grant (MOE2014-T2-1- 080) and A*STAR JCO grant (1431AFG100). This work at Yonsei University was supported by the Global Frontier R&D Program on Center for Multiscale Energy System funded by the National Research Foundation under the Ministry of Science, ICT & Future, Korea (NRF-2014M3A6A7060583). We thank Dr. Tan Geok Kheng and Dr. Bruno Donnadieu for the crystallographic analysis.
PublisherAmerican Chemical Society (ACS)
JournalThe Journal of Organic Chemistry
Is Supplemented ByHu, P., Lee, S., Park, K. H., Das, S., Herng, T. S., Gonçalves, T. P., … Wu, J. (2016). CCDC 1418608: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1jm5kw
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