Direct alkylthio-functionalization of unsubstituted perylenediimides

Abstract

Herein, we report a simple fluoride-mediated reaction for the direct mono- and dialkylthio-functionalization of unsubstituted perylenediimides (PDIs) under very mild conditions. The aromatic substitution reaction offers the possibility to introduce primary, secondary and, even, tertiary alkanethiols either on the 1- or on the 1,6-bay positions of unsubstituted PDIs. 1,6-DialkylthioPDIs show that absorption and fluorescence spectra shifted to the red when compared with the unsubstituted PDI, with Stokes shifts around 70-80 nm.

Progress in the synthesis of perylene bisimide dyes

“…Another means to access bay-alkoxylated PBIs from coreunsubstituted PBIs is by fluoride-mediated alkoxylation as proposed by Fernández-Lázaro and co-workers. 173 This reaction, as well as the analogous thiolation, 174 has, however, some limitations. Firstly, the scope of this novel reaction is still limited and the introduction of alkoxy or thio substituents occurs preferably for alkyl starting materials rather than aryl counterparts.…”

“…173 Likewise, introduction of two tert-butylthio substituents into bay areas was lowyielding, while the reaction of core-unsubstituted PBI with ethanedithiol, which was otherwise successful for halogenated precursors (see Scheme 30), proved ineffective. 174 It is also interesting to note that even for halogenated PBIs, fluorideassisted reactions with thiophenols are not well-suited as the yields are mediocre, whereas direct functionalization of the PBI core with thiophenols did not proceed at all. 174 Secondly, the reactions are not regioselective and twofold functionalization typically provides inseparable mixtures of 1,6 and 1,7regioisomers.…”

“…174 It is also interesting to note that even for halogenated PBIs, fluorideassisted reactions with thiophenols are not well-suited as the yields are mediocre, whereas direct functionalization of the PBI core with thiophenols did not proceed at all. 174 Secondly, the reactions are not regioselective and twofold functionalization typically provides inseparable mixtures of 1,6 and 1,7regioisomers.…”

Influence of Blending Ratio and Polymer Matrix on the Lasing Properties of Perylenediimide Dyes

“…The synthesis of the b-PDI-A derivative has been carried out for the first time in almost quantitative yield by substitution of the dibromoperylene derivative with diphenylphenol in the presence of CsF and 18-crown-6, using our previously described method (Scheme 1). 41 b-PDI-A was characterized by standard techniques such as 1 H-NMR, 13 C-NMR (See Figure S6 in the Supporting Information) and UV-vis spectroscopies, and high resolution MALDI-TOF spectrometry.…”

Self-assembly, optical and electrical properties of perylene diimide dyes bearing unsymmetrical substituents at bay position

“…However, substitution at the imide position can not affect the properties and electronic structures of PDIs, because the nodes in both lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) levels limit the electronic interactions between PDI and corresponding substituents 24 . Many literatures regarding modification of PDI derivatives at imide positions to generate self-assembled nanostructures have been reported 25 , 26 . However, few literature reported the self-assembly of bay area substituted PDI derivatives although substituents at bay area can dramatically change the electronic structures and photochemical properties of PDIs 27 .…”