PDF herunterladen
Synlett 2021; 32(18): 1855-1860
DOI: 10.1055/a-1628-5664
letter

Synthesis of Unsymmetrically Functionalized Violanthrenes by Reductive Aromatization of Violanthrone 79

Simon Werner
a   Chemistry Department, Philipps-University of Marburg, Hans-Meerwein Straße 4, 35043 Marburg, Germany
,
Jörg Sundermeyer∗
b   Chemistry Department and Materials Science Centre (WZMW), Philipps-University of Marburg, Hans-Meerwein Straße 4, 35043 Marburg, Germany
› InstitutsangabenFinancial support by the LOEWE Program of Excellence of the Federal State of Hesse (LOEWE Focus Group PriOSS ‘Principles of On-Surface Synthesis’) is gratefully acknowledged.
› Weitere Informationen
    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

The commercially available n-type semiconductive dye Violanthrone 79 was used as starting material to synthesize previously unexplored substituted violanthrenes through a reductive aromatization and functionalization strategy. By using the low-cost reducing agents zinc and sodium dithionite in combination with suitable electrophilic trapping reagents, three violanthrenes functionalized with two pivalyloxy, trimethylsiloxy, or methoxy groups were selectively obtained in high yields. Due to their octyl ether moieties, these new red dyes are highly soluble. They were characterized by means of UV/vis and fluorescence spectroscopy, and their redox properties were studied by cyclic voltammetry. The spectroscopically determined frontier molecular orbital energies are compared to those calculated by density functional theory and suggest that electron-deficient Violanthrone 79 was transformed into three electron-rich violanthrenes with molecular characteristics typically observed in molecular precursors for p-type organic semiconductors.

Key words

arenes - violanthrenes - electron transfer - polycycles - reduction - dyes

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1628-5664.
  • Supporting Information


Publikationsverlauf

Eingereicht: 23. Juli 2021

Angenommen nach Revision: 01. September 2021

Accepted Manuscript online:
01. September 2021

Artikel online veröffentlicht:
22. September 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 2 Shi M.-M, Chen Y, Nan Y.-X, Ling J, Zuo L.-J, Qiu W.-M, Wang M, Chen H.-Z. J. Phys. Chem. B 2011; 115: 618
    CrossrefPubMedSuche in Google Scholar
  • 3 Introduction to Organic Electronic and Optoelectronic Materials and Devices. Sun S.-S, Dalton LR. CRC Press; Boca Raton: 2008
    CrossrefSuche in Google Scholar
    • 4a Stepanenko V, Stocker M, Müller P, Büchner M, Würthner F. J. Mater. Chem. 2009; 19: 6816
      CrossrefSuche in Google Scholar
    • 4b Graser F, Hädicke E. Liebigs Ann. Chem. 1980; 1994
    • 4c Malenfant PR. L, Dimitrakopoulos CD, Gelorme JD, Kosbar LL, Graham TO, Curioni A, Andreoni W. Appl. Phys. Lett. 2002; 80: 2517
      CrossrefSuche in Google Scholar
  • 5 Akamatu H, Inokuchi H. J. Chem. Phys. 1950; 18: 810
    CrossrefPubMedSuche in Google Scholar
  • 6 Chung DS, Park JW, Park J.-H, Moon D, Kim GH, Lee H.-S, Lee DH, Shim H.-K, Kwon S.-K, Park CE. J. Mater. Chem. 2010; 20: 524
    CrossrefSuche in Google Scholar
  • 7 Cyran JD, Krummel AT. J. Chem. Phys. 2015; 142: 212435
    CrossrefPubMedSuche in Google Scholar
  • 10 Stallmann O, Wentz WM. US 2148042, 1938
  • 11 Scottish Dyes Ltd. DE 601753, 1929
  • 12 Münster W, Müller J. US 2249973, 1939
  • 14 Feofanov M, Akhmetov V, Sharapa DI, Amsharov K. Org. Lett. 2020; 22: 5741
    CrossrefPubMedSuche in Google Scholar
  • 15 Castellan A, Daney M, Desvergne J.-P, Riffaud M.-H, Bouas-Laurent H. Tetrahedron Lett. 1983; 24: 5215
    CrossrefSuche in Google Scholar
  • 16 VE3 Me3SiCl (0.4 mL, 3.2 mmol, 16 equiv) was added to a mixture of VO79 (142 mg, 0.20 mmol, 1.0 equiv) and Zn dust (209 mg, 3.20 mmol, 16 equiv) in 1,4-dioxane (10 mL), and the mixture was heated at 80 °C under argon for 18 h while the suspension turned red. When the reaction was complete (TLC), all volatilities were removed in vacuo and the residue was taken up in hexane (20 mL). The mixture was filtered and the product was precipitated at –80 °C then dried in a vacuum to give a red powder; yield: 137 mg (0.16 mmol, 80%). The reaction was also performed on a 1 mmol scale; yield: 660 mg (0.77 mmol, 77%). IR (ATR): 3071 (w), 2925 (s), 2855 (m), 1578 (w), 1494 (w), 1462 (w), 1348 (s), 1314 (m), 1260 (w), 1033 (vs), 876 (vs), 756 (s), 628 (w) cm–1. 1H NMR (300.1 MHz, CDCl3): δ = 0.44 [s, 18 H, Si(CH 3)3], 0.82–0.85 (m, 6 H, HOct ), 1.20–1.40 (m, 18 H, HOct ), 1.50–1.55 (m, 4 H, HOct ), 1.97 (quint, 3 J H,H = 7.5 Hz, 4 H, HOct ), 4.19–4.24 (m, 2 H, OCH 2), 4.53–4.58 (m, 2 H, OCH 2), 7.78–7.88 (m, 4 H, H3, H4), 8.37 (d, 3 J H,H = 9.6 Hz, 2 H, H6), 8.41 (s, 2 H, H1), 8.56 (dd, 3 J H,H = 9.4 Hz, 4 J H,H = 2.6 Hz, 2 H, H2), 8.75 (d, 3 J H,H = 9.7 Hz, 2 H, H7), 9.05 (dd, 3 J H,H = 9.2, 4 J H,H = 2.0 Hz, 2 H, H5). 13C NMR (75.5 MHz, CDCl3): δ = 1.2, 14.2, 22.8, 26.4, 29.5, 29.7, 29.9, 32.0, 69.0, 101.5, 117.8, 119.9, 120.0, 122.2, 123.0, 123.7, 123.8, 125.1, 125.4, 125.7, 125.8, 126.2, 126.6, 128.8, 144.8, 156.0. HRMS (LIFDI+): m/z [M+] calcd for C56H66O4Si2: 858.44996; found: 858.44898.
  • 17 Nakazato T, Kamatsuka T, Inoue J, Sakurai T, Seki S, Shinokubo H, Miyake Y. Chem. Commun. 2018; 54: 5177
    CrossrefPubMedSuche in Google Scholar
  • 18 Nakamura Y, Nakazato T, Kamatsuka T, Shinokubo H, Miyake Y. Chem. Eur. J. 2019; 25: 10571
    CrossrefPubMedSuche in Google Scholar
  • 19 VE1 Pivalic anhydride (0.4 mL, 3.5 mmol, 16 equiv) was added to a mixture of VO79 (158 mg, 0.22 mmol, 1.0 equiv) and Zn dust (230 mg, 3.52mmol, 16 equiv) in 1,4-dioxane (15 mL), and the mixture was refluxed under argon for 18 h while the suspension turned brownish red. When the reaction was complete (TLC), the suspension was filtered, and all volatilities were removed in vacuo. The residue was taken up in CH2Cl2 (20 mL) and filtered over neutral alumina. The product was precipitated from hexane at –80 °C and dried in vacuo to give a red powder; yield: 163 mg (0.19 mmol, 85%). IR (ATR): 2926 (m), 2858 (m), 1751 (s), 1582 (w), 1516 (w), 1430 (w), 1383 (w), 1215 (m), 1109 (vs), 1031 (w), 787 (w), 637 (w) cm–1. 1H NMR (300.1 MHz, CDCl3): δ = 0.79–0.85 (m, 6 H, HOct ), 1.20–1.43 (m, 18 H, HOct ), 1.47–1.53 (m, 4 H, HOct ), 1.74 [s, 18 H, C(CH 3)3], 1.96 (quint, 3 J H,H = 7.1 Hz, 4 H, HOct ), 4.15–4.25 (m, 2 H, OCH 2), 4.50–4.62 (m, 2 H, OCH 2), 7.79–7.89 (m, 4 H, H3, H4), 7.99 (d, 3 J H,H = 9.6 Hz, 2 H H6), 8.19 (dd, 3 J H,H = 9.2, 4 J H,H = 1.6 Hz, 2 H, H2), 8.42 (s, 2 H, H1), 8.71 (d, 3 J H,H = 9.6 Hz, 2 H, H7), 9.07 (dd, 3 J H,H = 8.6, 4 J H,H = 1.1 Hz, 2 H, H5). 13C NMR (75.5 MHz, CDCl3): δ = 14.2, 22.8, 26.3, 26.7, 27.9, 29.5, 29.7, 29.8, 31.9, 40.0, 69.0, 101.7, 118.0, 118.9, 121.3, 121.5, 122.0, 123.9, 124.0, 125.6, 125.7, 125.7, 126.0, 126.9, 128.0, 128.5, 139.4, 156.8, 177.5. HRMS (APCI+): m/z [M + H]+ Calcd for C60H67O6: 883.4932; found: 883.4953.
  • 20 VE2
    VO79     (142 mg, 0.20 mmol, 1.0 equiv), KOH (400 mg; excess), and Na2S2O4 (279 mg, 1.60 mmol, 8.0 equiv) were dissolved in toluene (10 mL) and H2O (10 mL). Aliquat 336 (0.1 mL) was added, and the mixture was stirred for 1 h at 90 °C then cooled to r.t. MeI (0.12 mL, 2.0 mmol, 10 equiv) was added and the mixture was stirred for 30 min at 90 °C. When the reaction was complete (TLC), the organic phase was collected, dried (MgSO4), filtered, and concentrated. The residue was taken up in CH2Cl2 (20 mL) and filtered over neutral alumina. The product was the precipitated at –80 °C from hexane and dried in vacuo to give a red powder; yield: 110 mg (0.15 mmol, 75%). IR (ATR), 3069 (m), 2926 (vs), 2854 (s), 1581 (m), 1492 (m), 1426 (w), 1345 (m), 1211 (vs), 1068 (m), 973 (w), 790 (m), 632 (w) cm–1. 1H NMR (300.1 MHz, CDCl3): δ = 0.75–0.90 (m, 6 H, HOct ), 1.18–1.45 (m, 18 H, HOct ), 1.45–1.55 (m, 4 H, HOct), 1.97 (quint, 3 J H,H = 7.7 Hz, 4 H, HOct), 4.15–4.25 (m, 2 H, OCH2), 4.28 (s, 6 H, OCH3), 4.45–4.65 (m, 2 H, OCH2), 7.82–7.90 (m, 4 H, H3, H4), 8.43 (s, 2 H, H1), 8.48 (d, 3 J H,H = 9.5 Hz, 2 H, H6), 8.62 (dd, 3 J H,H = 9.5, 4 J H,H = 4.2 Hz, 2 H, H2), 8.82 (d, 3 J H,H = 9.7 Hz, 2 H, H7), 9.08 (dd, 3 J H,H = 9.5, 4 J H,H = 4.3 Hz, 2 H, H5). 13C NMR (75.5 MHz, CDCl3): δ = 14.2, 22.8, 26.4, 29.5, 29.7, 29.9, 31.7, 31.9, 63.7, 69.0, 101.6, 117.8, 119.5, 122.3, 123.0, 123.2, 124.0, 125.7, 125.9, 126.1, 126.4, 126.7, 128.9, 156.5. HRMS (LIFDI+): m/z [M+] Calcd for C52H54O4: 742.40221; found: 742.40214.
  • 22 Nichols VM, Rodriguez MT, Piland GB, Tham F, Nesterov VN, Youngblood WJ, Bardeen CJ. J. Phys. Chem. C 2013; 117: 16802
    CrossrefSuche in Google Scholar
  • 23 Würthner F, Saha-Möller CR, Fimmel B, Ogi S, Leowanawat P, Schmidt D. Chem. Rev. 2016; 116: 962
    CrossrefPubMedSuche in Google Scholar
  • 24 Lakowicz JR. Principles of Fluorescence Spectroscopy, 3rd ed. Springer; Boston: 2006
    Suche in Google Scholar
  • 25 Klán P, Wirz J. Photochemistry of Organic Compounds: From Concepts to Practice. Wiley; Chichester: 2009
    Suche in Google Scholar
  • 26 D’Andrade BW, Datta S, Forrest SR, Djurovich P, Polikarpov E, Thompson ME. Org. Electron. 2005; 6: 11
    CrossrefSuche in Google Scholar