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. 2023 Feb 16;29(10):e202203405.
doi: 10.1002/chem.202203405. Epub 2022 Dec 29.

Edge-Decorated Polycyclic Aromatic Hydrocarbons by an Oxidative Coupling Approach

Philip Gilmartin  1 , Cassandra Vu  1 , Madeline Rotella  1 , Jasjit Kaur  1 , Marisa Kozlowski  1
Affiliations

Edge-Decorated Polycyclic Aromatic Hydrocarbons by an Oxidative Coupling Approach

Philip Gilmartin et al. Chemistry. .

Abstract

Oxidative phenol coupling reduces reliance on halo/metalated substrates used in conventional redox neutral couplings. A new strategy for constructing polycyclic aromatic hydrocarbons (PAHs) that incorporates oxidative phenol coupling is outlined in a three-stage approach: oxidative fragment coupling, linking of the two resultant units, and oxidative cyclization. The protocol allows rapid assembly of both planar and helical systems with a high degree of edge functionalization. The incorporation of 12 alkoxy groups on systems with 12 rings gave rise to lower optical gaps compared to systems with a lesser degree of edge functionalization.

Keywords: organic synthesis; oxidative cross coupling; polycyclic aromatic hydrocarbons.

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Figures

Figure 1:
Figure 1:
Examples of previously synthesized PAHs illustrating important structural features.
Figure 2.
Figure 2.
Coventional approaches (a) Suzuki cross coupling b) Diels-Alder reaction to building PAH framework vs. our work (c) oxidative cross coupling.
Figure 3.
Figure 3.
Cyclic voltammograms of selected PAHs with first oxidation potentials reported. Voltammograms obtained using a glassy carbon working electrode, a platinum counter electrode, and a silver wire reference electrode, scanned from 0 to 1.6 V and plotted using polarographic convention.
Figure 4.
Figure 4.
Normalized UV-Visible absorption spectra for selected compounds.
Figure 5.
Figure 5.
Normalized emission spectra for selected compounds.
Figure 6.
Figure 6.
Comparison of band gaps and quantum yield to previously reported PAHs
Figure 7.
Figure 7.
Geometry optimized structures for selected PAHs a) 14a b) 14f c) 14g d) 14n.
Scheme 1.
Scheme 1.
Initial synthesis of tetra-alkoxy building block.
Scheme 2.
Scheme 2.
Preferred site of bond formation for precursors 6 and 10. a) Cyclodehydrogenation of 6b - dealkylation and dienone formation b) Cyclodehydrogentation versus dearomatization c) Alkoxy substitution favoring cyclodehydrogenation.
Scheme 3.
Scheme 3.
Synthesis of hexa-alkoxy dibenzopyrene precursors.
Scheme 4.
Scheme 4.
Building block approach to π-extended PAHs using bis-boron linkers.
Scheme 5.
Scheme 5.
Bis-suzuki coupling with building block 9b. a) Cross coupling using linear linkers b) Cross coupling using angular linkers.
Scheme 6.
Scheme 6.
Cyclodehydrogenation of PAH precursors to access PAHs. *Decomposed on silica gel.
See this image and copyright information in PMC

References

    1. Feng X, Pisula W, Müllen K, Pure Appl. Chem 2009, 81, 2203–2224;
    2. Gowda A, Kumar M, Kumar S, Liq. Cryst 2017, 44, 1990–2017;
    3. Harvey R, Wiley-VCH, 1997;
    4. Kumar S, Tao Y-T, Chem. - Asian J 2021, 16, 621–647; - PubMed
    5. Miao Q, Wiley-VCH, Weinheim, Germany, 2015;
    6. Tran-Van A-F, Wegner HA, in Polyarenes I (Eds.: Siegel JS, Wu Y-T), Springer; Berlin Heidelberg, Berlin, Heidelberg, 2014, pp. 121–157;
    7. Wang X-Y, Yao X, Müllen K, Sci. China: Chem 2019, 62, 1099–1144.
    1. Sergeyev S, Pisula W, Geerts YH, Chem. Soc. Rev 2007, 36, 1902–1929. - PubMed
    1. Kumar S, Liq. Cryst 2004, 31, 1037–1059;
    2. Pal SK, Setia S, Avinash BS, Kumar S, Liq. Cryst 2013, 40, 1769–1816.
    1. He J, Agra-Kooijman DM, Singh G, Wansg C, Dugger C, Zeng J, Zang L, Kumar S, Hartley CS, J. Mater. Chem. C 2013, 1, 5833–5836;
    2. Zhao K-Q, Jing M, An L-L, Du J-Q, Wang Y-H, Hu P, Wang B-Q, Monobe H, Heinrich B, Donnio B, J. Mater. Chem. C 2017, 5, 669–682.
    1. Dou X, Yang X, Bodwell GJ, Wagner M, Enkelmann V, Müllen K, Org. Lett 2007, 9, 2485–2488; - PubMed
    2. Wadumethrige SH, Rathore R, Org. Lett 2008, 10, 5139–5142; - PubMed
    3. Wang Z, Dötz F, Enkelmann V, Müllen K, Angew. Chem. Int. Ed 2005, 44, 1247–1250. - PubMed

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