Synthesis and Self-Assembly Behavior of Double Ullazine-Based Polycyclic Aromatic Hydrocarbons

Marcus Richter; Michal Borkowski; Yubin Fu; Evgenia Dmitrieva; Alexey Popov; Ji Ma; Tomasz Marszalek; Wojciech Pisula; Xinliang Feng

doi:10.1055/a-1472-6852

Organic Materials, Table of Contents

CC BY-NC-ND 4.0 · Organic Materials 2021; 03(02): 198-203
DOI: 10.1055/a-1472-6852

Focus Issue: Peter Bäuerle 65th Birthday

Short Communication

Synthesis and Self-Assembly Behavior of Double Ullazine-Based Polycyclic Aromatic Hydrocarbons

Marcus Richter

^aChair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany

,

Michal Borkowski

^bDepartment of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland

,

Yubin Fu

^aChair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany

,

Evgenia Dmitrieva

^cCenter of Spectroelectrochemistry, Nanoscale chemistry, Leibniz Institute for Solid State and Materials Research (IFW), Helmholtzstrasse 20, 01069 Dresden, Germany

,

Alexey Popov

^cCenter of Spectroelectrochemistry, Nanoscale chemistry, Leibniz Institute for Solid State and Materials Research (IFW), Helmholtzstrasse 20, 01069 Dresden, Germany

,

Ji Ma

^aChair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany

,

Tomasz Marszalek

^bDepartment of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland

^dMax Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany

,

Wojciech Pisula

^bDepartment of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland

^dMax Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany

,

Xinliang Feng

^aChair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany

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Abstract

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Abstract

Polycyclic aromatic azomethine ylides (PAMY, 1) are versatile building blocks for the bottom-up synthesis of nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Although the chemistry of PAMY was already established few years ago, the cycloaddition of a double PAMY building block has not been reported so far. In this work, we demonstrate the first cycloaddition of a PAMY-dimer (6), which opens the access to three different alkyl ester-substituted N-PAHs with a laterally extended double ullazine scaffold (DU-1, DU-2 and DU-3). Interestingly, the cyclic voltammetry of DU-1–3 exhibited three reversible oxidation waves, which confirmed the electron-rich nature of the double ullazine scaffold. Furthermore, in situ spectroelectrochemistry study of ethylhexyl ester-substituted DU-3 revealed the formation of different cationic species with new absorption bands up to 1689 nm. Additionally, the influence of the attached substituents on the film formation and supramolecular organization in the thin films was investigated by polarized optical microscopy and grazing incidence wide-angle X-ray scattering.

Key words

polycyclic aromatic hydrocarbons - nanographenes - polycyclic aromatic azomethine ylides - cycloaddition - ullazine

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References

References and Notes

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11 Synthetic procedure for iminium salt (8): In a microwave tube, the tetra-alcohol species (7, 0.1 g, 188 µmol) was added into a stirring anhydrous hydrogen chloride solution (4 M in dioxane, 5 mL). The microwave tube was capped and placed in a microwave reactor. A dynamic mode was chosen (300 W, power max: on, activated cooling, pre-stirring: 10 s, temperature: 130 °C) for 1.5 h. After cooling to room temperature, the cap was removed and the reaction mixture was transferred to a round-bottom flask. The solvents were removed under reduced pressure. The crude product was dissolved in toluene (anhydrous, 20 mL) and heated to 90 °C under argon. In a second dry and inert Schlenk flask, triphenylcarbenium tetrafluoroborate was dissolved in anhydrous acetonitrile and added dropwise. After continuous stirring for 2 h, the solvents were removed under reduced pressure. The residue was dissolved in DCM and precipitated in diethyl ether (250 mL). The crude product 8 was obtained as a yellow solid. HR-MS (MALDI-ToF):m/z ([M + H]⁺ ) = 459.1893, calcd. for C₃₄H₂₃N₂: m/z = 459.1861, error = 6.96 ppm
12 General synthetic procedure of DU-1–3: In a dry and inert Schlenk flask, crude 8 (100 mg) and the corresponding dipolarophiles were dissolved in anhydrous chloroform. At 60 °C, the addition of triethylamine was carried out in one shot and the reaction mixture was kept under continuous stirring overnight. After cooling to room temperature, the reaction mixture was transferred into a round-bottom flask and the solvent was removed under reduced pressure. After the addition of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) the round-bottom flask was sealed and purged with argon. Anhydrous toluene was added and the reaction mixture was stirred for 3 h. The reaction was quenched with water and extracted with dichloromethane (50 mL, 5 times). The solvent was removed under reduced pressure. The crude product was dissolved in a small amount of dichloromethane and precipitated in methanol (250 mL). After the filtration, the crude product was purified by column chromatography on silica in pure chloroform and via rGPC. The target compounds DU-1–3 were obtained as yellow solids. DU-1:¹H-NMR (600 MHz, C₂D₂Cl₄): δ 9.71 (s, 2 H), 8.25 (d, J = 8.2 Hz, 2 H), 8.19 (d, J = 8.0 Hz, 2 H), 8.01 (d, J = 8.0 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 2 H), 7.58 (t, J = 7.7 Hz, 2 H), 7.32 (t, J = 7.5 Hz, 2 H), 7.23 (t, J = 7.3 Hz, 2 H), 4.49 (t, J = 7.0 Hz, 4 H), 4.42 (t, J = 7.0 Hz, 4 H), 1.83 (td, J = 14.5, 7.2 Hz, 12 H), 1.53–1.40 (m, 8 H), 1.38–1.30 (m, 8 H), 1.29–1.25 (m, 4 H), 1.24–1.12 (m, 40 H), 0.77 (dt, J = 21.0, 7.0 Hz, 12 H). ¹³C-NMR (151 MHz, C₂D₂Cl₄): δ 167.2, 166.2, 128.6, 128.0, 127.9 127.6, 125.7, 125.6, 124.6, 123.8, 123.0, 122.1, 122.0, 121.4, 32.2, 30.0, 29.9, 29.8, 29.7, 29.2, 29.0, 26.5, 23.0, 14.5. HR-MS (MALDI-ToF): m/z ([M]⁺ ) = 1240.7471, calcd. for C₈₂H₁₀₀N₂O₈: m/z = 1240.7479, error = −0.7 ppm. IR: ṽ = 2921, 2853, 1713, 1195, 1128, 747 cm⁻¹. DU-2:¹H-NMR (600 MHz, C₂D₂Cl₄): 9.54 (s, 2 H), 8.10 (d, J = 7.5 Hz, 2 H), 8.04 (d, J = 7.6 Hz, 2 H), 7.85 (d, J = 7.3 Hz, 2 H), 7.72 (d, J = 7.2 Hz, 2 H), 7.47 (t, J = 7.2 Hz, 2 H), 7.21 (t, J = 7.0 Hz, 2 H), 7.10 (t, J = 6.5 Hz, 2 H), 4.48–4.40 (m, 7 H), 4.40–4.27 (m, 8 H), 1.79 (d, J = 6.8 Hz, 8 H), 1.42 (d, J = 6.1 Hz, 8 H), 1.37–1.25 (m, 8 H), 1.12 (dd, J = 28.9, 25.8 Hz, 60 H), 0.72 (dd, J = 16.3, 6.8 Hz, 12 H). ¹³C-NMR (151 MHz, C₂D₂Cl₄): δ 167.54, 166.39, 128.55, 127.94, 127.87, 126.50, 126.22, 125.64, 124.50, 124.07, 123.80, 123.42, 122.26, 122.20, 122.03, 121.32, 120.57, 120.07, 74.20, 32.20, 30.02, 30.00, 29.98, 29.93, 29.80, 29.67, 29.16, 29.03, 26.55, 26.52, 23.00, 14.51, 14.50. HR-MS (MALDI-ToF): m/z ([M]⁺ ) = 1352.8741, calcd. for C₉₀H₁₁₆N₂O₈: m/z = 1352.8731, error = 0.7 ppm. IR: ṽ = 2918, 2851, 1713, 1194, 1126, 747 cm⁻¹. DU-3:¹H-NMR (600 MHz, C₂D₂Cl₄): δ 9.78 (s, 2 H), 8.39 (dd, J = 24.5, 6.4 Hz, 4 H), 8.24 (d, J = 6.7 Hz, 2 H), 8.16 (s, 2 H), 7.69 (t, J = 7.5 Hz, 2 H), 7.42 (s, 4 H), 5.28–5.21 (m, 2 H), 5.17–5.04 (m, 2 H), 1.86–1.61 (m, 20 H), 1.34 (d, J = 37.1 Hz, 12 H), 1.26–1.14 (m, 12 H), 1.08 (d, J = 2.8 Hz, 8 H), 1.01–0.89 (m, 12 H), 0.81 (d, J = 1.1 Hz, 6 H), 0.66 (d, J = 6.2 Hz, 6 H). ¹³C-NMR (151 MHz, C₂D₂Cl₄): δ 166.84, 166.79, 128.82, 128.68, 128.17, 127.11, 126.64, 126.62, 125.73, 125.72, 125.26, 125.24, 125.22, 124.67, 124.24, 124.14, 123.78, 123.27, 123.25, 122.87, 122.31, 122.29, 121.77, 120.13, 120.10, 116.85, 114.87, 114.38, 114.35, 74.20, 33.56, 33.46, 32.91, 32.11, 32.00, 29.80, 29.67, 26.83, 26.17, 25.72, 25.51, 22.98, 22.89, 14.51, 14.37, 10.06, 9.82. HR-MS (MALDI-ToF): m/z ([M]⁺ ) = 1184.6855, calcd. for C₇₈H₉₂N₂O₈: m/z = 1184.6853, error = 0.1 ppm. IR: ṽ = 2954, 2924, 2858, 1703, 1194, 744 cm⁻¹
13 Osaka I, Zhang R, Sauvé G, Smilgies D.-M, Kowalewski T, McCullough RD. J. Am. Chem. Soc. 2009; 131: 2521

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