Synthesis of 1,6/7‐(NO₂)₂‐Perylenediimide and 1,6/7‐(NH₂)₂‐Perylenediimide as Regioisomerically Pure Materials**

Abstract

The use of perylenediimide (PDI) building blocks in materials for organic electronic is of considerable interest. This popular n-type organic semiconductor is tuned by introducing peripheral groups in their ortho and bay positions. Such modifications radically alter their optoelectronic properties. In this article, we describe an efficient method to afford regioisomerically pure 1,6/7-(NO 2 ) 2 -and (NH 2 ) 2 -PDIs employing two key steps: the selective crystallization of 1,6-(NO 2 ) 2 -perylene-3,4,9,10-tetracarboxy tetrabutylester and the nitration of regiopure 1,7-Br 2 -PDI with silver nitrite. The optoelectronic properties of the resulting regioisomerically pure dinitro, diamino-PDIs and bisazacoronenediimides (BACDs) are reported and demonstrate the need to separate both regioisomers of such n-type organic semiconductors for their inclusion in advanced optoelectronic devices. For the first time, the two regioisomers of the same PDI starting material are available on the multigram scale, which will stimulate the exploration of regioisomerism/ properties relationship for this family of dyes.

ortho O-Annulated azabenzannulated perylenediimide and bisazacoronenediimide

“…A non-symmetrical O -annulated BACD dimer with a central phenyl ring was prepared. The sequence involved a double visible-light azabenzannulation between regiopure 23 1,6-(NH 2 ) 2 PDI 8 and isophthalaldehyde to obtain an amine-terminated dimer, subsequently reacted with an excess of salicylaldehyde in another azabenzannulation reaction. Finally, the intermediate was engaged in copper-catalysed oxidative C–H activation to afford dimer 9 in a very good (45%) overall yield following seven synthetic steps.…”

“…This flexibility has been considered in the calculation of the optical properties. As already observed in our previous study, 23 the lateral chains were not considered as they do not have an influence on the optical properties and thus compounds 2a and 2b were equivalent for the computational part and denoted as 2 . For all compounds, the lateral chains were replaced with a methyl group.…”

Dynamic Covalent Synthesis Applied to Optoelectronic and Energy Materials: Design, Applications and Limitations

“…The power conversion efficiency (PCE) of these organic photovoltaic devices reached 1.9 % on blends of azabenzannulated PDI multimers 8 with the PM6 polymer. [55] In addition, employing two consecutive light-driven azabenzannulation reactions followed by a post-functionalization reaction on regiopure 1,6diamino-PDI, [56] we were able to synthesize a bis-azacoronene diimide (BACD) dimer 9 doped with oxygen atoms (Figure 7c). The electron-poor compound 9 was exploited as a NFA in bulkheterojunction OSCs.…”