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Synlett 2021; 32(18): 1855-1860
DOI: 10.1055/a-1628-5664
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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
› Author AffiliationsFinancial 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.
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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


Publication History

Received: 23 July 2021

Accepted after revision: 01 September 2021

Accepted Manuscript online:
01 September 2021

Article published online:
22 September 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
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