Controllable Monobromination of Perylene Ring System: Synthesis of Bay-Functionalized Perylene Dyes

Abstract

Practical synthesis of bay-monofunctionalized perylene dyes has been developed based on controllable NBS bromination of tetrabenzyl perylene-3,4,9,10-tetracarboxylate. The ability to perform the convenient and high-yielding synthesis highlights the potential utility of our multifunctional approach to access a diverse range of new perylene systems.

Modular Synthesis and Structure–Property Correlation of Pyrene – Rylene Dyes for Cellular Imaging

“…The synthetic methods for 1,6‐diethynylpyrene, 1,3,6,8‐tetraethynylpyrene, 1‐bromotetra‐ n ‐butyl perylene‐3,4,9,10‐tetracarboxylate (PTE‐Br) and 4‐bromo‐ n ‐butyl‐1,8‐naphthalimide (NMI‐Br) precursors were adopted from previously reported methods. The syntheses of the target compounds were achieved from the appropriate starting materials using PdCl 2 (PPh 3 ) 2 and CuI as catalyst and co‐catalyst under mild basic conditions (Scheme ).…”

Regioselective Bay‐Functionalization of Perylenes Toward Tailor‐Made Synthesis of Acceptor Materials for Organic Photovoltaics

“…All solvents and reagents were of reagent grade quality from Wako Pure Chemicals and Tokyo Chemical Industry (TCI) used without further purification. The requisite synthetic intermediates 1 , 5 and the reference sample 15 were prepared according to the literatures . The OPV devices were fabricated on indium tin oxide (ITO)‐coated glass substrates (ITO thickness: 150 nm; sheet resistance: 10.3 Ω sq −1 ; Techno Print).…”

“…The requisite synthetic intermediates 1, 5 and the reference sample 15 were prepared according to the literatures. [9] The OPV devices were fabricated on indium tin oxide (ITO)-coated glass substrates (ITO thickness: 150 nm; sheet resistance: 10.3 Ω sq À 1 ; Techno Print). The ITO substrates were cleaned by UV-O 3 treatment for 20 min.…”

“…Such synthetic limitation has impeded rapid feedbacks of mechanistic investigation on OPV performance into superior design of the PDI‐based NFAs, despite the potential advantages of the structural versatility. In this regard, we recently developed highly controllable monobromination of tetrabenzyl perylene‐3,4,9,10‐tetracarboxylate 1 to obtain the corresponding bromide 2 (Scheme ) with an isolated yield of 83 % . Due to high solubility and reactivity, this type of perylene tetraesters (PTEs) provided the enhanced synthetic utility for the bromination‐based bay‐functionalization.…”

“…In this regard, we recently developed highly controllable monobromination of tetrabenzyl perylene-3,4,9,10-tetracarboxylate 1 to obtain the corresponding bromide 2 (Scheme 1) with an isolated yield of 83 %. [9] Due to high solubility and reactivity, [10] this type of perylene tetraesters (PTEs) provided the enhanced synthetic utility for the bromination-based bay-functionalization. At this point, it was expected that the synthetic method would open the way for mechanistic study to answer the question like what is the key molecular structure to reduce voltage loss, which is the most important topic nowadays to enhance the OPV performance further.…”