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

a   Chair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany
,
b   Department of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland
,
a   Chair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany
,
c   Center of Spectroelectrochemistry, Nanoscale chemistry, Leibniz Institute for Solid State and Materials Research (IFW), Helmholtzstrasse 20, 01069 Dresden, Germany
,
c   Center of Spectroelectrochemistry, Nanoscale chemistry, Leibniz Institute for Solid State and Materials Research (IFW), Helmholtzstrasse 20, 01069 Dresden, Germany
,
Ji Ma
a   Chair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany
,
b   Department of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland
d   Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany
,
b   Department of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland
d   Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany
,
a   Chair for Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed), Faculty of Food Chemistry and Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01069 Dresden, Germany
› Author Affiliations
Funding Information This research was financially supported by the EU Graphene Flagship (Graphene Core 3, 881603), ERC Consolidator Grant (T2DCP, 819698), the German Research Foundation (DFG) within the Cluster of Excellence “Center for Advancing Electronics Dresden (cfaed)” and DFG-NSFC Joint Sino-German Research Project (EnhanceNano, No. 391979941), as well as the DFG-SNSF Joint Switzerland-German Research Project (EnhanTopo, No. 429265950). M. Borkowski and T. Marszalek acknowledge the Foundation for Polish Science financed by the European Union under the European Regional Development Fund (POIR.04.04.00-00-3ED8/17). W. Pisula acknowledges National Science Centre, Poland, through the grant UMO-2015/18/E/ST3/00322.


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.

Supporting Information

Supporting Information for this article is available online at https://doi.org/10.1055/a-1472-6852.


Dedicated to Professor Peter Bäuerle on the occasion of his 65th birthday.


Supporting Information



Publication History

Received: 26 January 2021

Accepted: 18 March 2021

Publication Date:
01 April 2021 (online)

© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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  • 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
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