Synthesis and Optoelectronic Characterization of Perylene Diimide-Quinoline Based Small Molecules

Abstract

Perylene diimide (PDI) is one of the most studied functional dyes due to their structural versatility and fine tuning of the materials properties. Core substituted PDIs are prominent n-type semiconductor materials that could be used as non-fullerene acceptors in organic photovoltaics. Herein, we develop versatile organic building blocks based on PDI by decorating the PDI core with quinoline groups. Styryl and hydroxy phenyl mono and difunctionalized molecules were prepared using mono-nitro and dibromo bay substituted PDIs by Suzuki coupling with the respective boronic acid derivatives. A novel methodology using nitro-PDI under Suzuki coupling conditions as an electrophile partner was successfully tested. Furthermore, the PDI derivatives were used for the synthesis of soluble, electron accepting small molecules combining PDI with weak electron withdrawing quinoline derivatives. The new molecules presented wide absorbance in the visible spectrum from 450 to almost 700 nm while their LUMO levels and their energy levels are in the range of −3.8 to −4.2 eV.

Nitro-Perylenediimide: An Emerging Building Block for the Synthesis of Functional Organic Materials

“…The versatility of this original SMC reaction was demonstrated by replacing the phenyl boronic acid substituted with the electron-withdrawing formyl group by the (4-diphenylamino)phenyl electron-donating group. In 2019, J. K. Kallistsis and co-workers applied the same conditions to functionalize the PDI with a protected phenoxy and a styryl moiety [67]. Those anchoring groups were subsequently used to attach withdrawing quinoline derivatives through Heck coupling or nucleophilic substitution after the alcohol deprotection.…”

Tackling Performance Challenges in Organic Photovoltaics: An Overview about Compatibilizers

“…Even if we mentioned conjugated polymers, the discussion should be extended to a wide collection of chromophores, which have been successfully tested; in particular, chromophores with small aromatic cores (naphthalenes [65], pyrenes [66], and perylenes [67]) are typical examples of discrete molecules that are easy to handle and precisely modify (unlike polymers), and they are able to create ordered nanostructures that resemble polymer chains (columns, stacks of lamellae), due to π-π stacking interactions. Some relevant efforts have focused on the engineering of π-conjugated macromolecules by direct arylation strategies for BHJs [68], fluoro-functionalized quinoxaline-based polymers to be used as low-band gap acceptors [69], and finally perylene diimides as n-type organic molecules usable as non-fullerene acceptors in organic photovoltaics [70]. Generally speaking, strong π-π interactions are desirable, since they allow for the propagation of excitons and/or charge carriers through relatively long distance (like in a polymer chain), although there is not a physical network of bonded atoms.…”

Perylene-Based Chromophore as a Versatile Dye for Light Amplification

“…PDIs find application as laser dyes due to their high luminescence efficiency [ 34 ]. According to the literature [ 35 ], PDIs can be considered as very useful materials due to the versatility of their chemical structure. Solubility, tunability, electronic, optical, and morphological features for PDIs may vary depending on the substituents in the ortho, bay, or imide positions.…”