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A Naphtho-p-quinodimethane Exhibiting Baird’s (Anti)Aromaticity, Broken Symmetry, and Attractive Photoluminescence

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Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616, United States
Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States
§ Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58106, United States
Department of Chemistry, Columbia University, New York, New York 10025, United States
Cite this: J. Org. Chem. 2017, 82, 19, 10167–10173
Publication Date (Web):August 24, 2017
https://doi.org/10.1021/acs.joc.7b01647
Copyright © 2017 American Chemical Society

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    Abstract

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    We report a novel reductive desulfurization reaction involving π-acidic naphthalene diimides (NDI) 1 using thionating agents such as Lawesson’s reagent. Along with the expected thionated NDI derivatives 26, new heterocyclic naphtho-p-quinodimethane compounds 7 depicting broken/reduced symmetry were successfully isolated and fully characterized. Empirical studies and theoretical modeling suggest that 7 was formed via a six-membered ring oxathiaphosphenine intermediate rather than the usual four-membered ring oxathiaphosphetane of 26. Aside from the reduced symmetry in 7 as confirmed by single-crystal XRD analysis, we established that the ground state UV–vis absorption of 7 is red-shifted in comparison to the parent NDI 1. This result was expected in the case of thionated polycyclic diimides. However, unusual low energy transitions originate from Baird 4nπ aromaticity of compounds 7 in lieu of the intrinsic Hückel (4n + 2)π aromaticity as encountered in NDI 1. Moreover, complementary theoretical modeling results also corroborate this change in aromaticity of 7. Consequently, photophysical investigations show that, compared to parent NDI 1, 7 can easily access and emit from its T1 state with a phosphorescence 3(7a)* lifetime of τP = 395 μs at 77 K indicative of the formation of the corresponding “aromatic triplet” species according to the Baird’s rule of aromaticity.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b01647.

    • Single-crystal XRD structure of 1b also deposited in the Cambridge Crystallographic Data Centre database with reference CCDC 1551374 (CIF)

    • Single-crystal XRD structures of 7b also deposited in the Cambridge Crystallographic Data Centre database with reference CCDC 1551375 (CIF)

    • Additional characterization (NMR, FTIR, TGA, and DSC spectra) of NDIs 16 and naphthoquinodimethanes 7, UV–Vis absorption, and supplementary photoluminescence data (PDF)

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