Synthesis, Photophysical and Electronic Properties of Mono‐, Di‐, and Tri‐Amino‐Substituted Ortho‐Perylenes, and Comparison to the Tetra‐Substituted Derivative

Abstract

We synthesized a series of new mono‐, di‐, tri‐ and tetra‐substituted perylene derivatives with strong bis(para‐methoxyphenyl)amine (DPA) donors at the uncommon 2,5,8,11‐positions. The properties of our new donor‐substituted perylenes were studied in detail to establish a structure‐property relationship. Interesting trends and unusual properties are observed for this series of new perylene derivatives, such as a decreasing charge transfer (CT) character with increasing number of DPA moieties and individual reversible oxidations for each DPA moiety. Thus, (DPA)‐Per possesses one reversible oxidation while (DPA)4‐Per has four. The mono‐ and di‐substituted derivatives display unusually large Stokes shifts not previously reported for perylenes. Furthermore, transient absorption measurements of the new derivatives reveal an excited state with lifetimes of several hundred microseconds, which sensitizes singlet oxygen with quantum yields of up to 0.83.

Modulating TTA efficiency through control of high energy triplet states

“…Perylene substitution has been previously explored in relation to solubility and mechanistic studies of aggregation. [35][36][37][38] Previous studies have investigated a library of substituted perylenes computationally and experimentally, with consideration given to their excited state energetics with differing functional groups, or multiple substitutions. 39 However, no systematic investigation has been carried out on the modulation of perylene photophysics with site selective substitution.…”

A Series of Soluble Planar Oligorylenes up to Hexarylene†

“…Synthetic route for hexarylene H is shown in Scheme 1. The aryl unit and tri‐borylated perylene 1 [ 9 ] were coupled by the Suzuki‐Miyaura cross‐coupling reaction in 62% yield. Triaryl perylene 2 was brominated with NBS to afford 3‐bromo‐triarylperylene 3 in 94% yield.…”

Electron‐Rich EDOT Linkers in Tetracationic bis‐Triarylborane Chromophores: Influence on Water Stability, Biomacromolecule Sensing, and Photoinduced Cytotoxicity

“…[92] The photosensitized production of singlet oxygen via organic molecules has been a very pertinent research field for many decades. [93][94][95][96][97][98][99][100][101][102][103][104][105][106] Singlet oxygen has found many applications, [107] for example, as a synthetic reagent, [108] an insecticide [109] and, perhaps most prominently, as a reactive oxygen species (ROS) leading to cell death in unwanted tissue via photodynamic therapy. [110][111][112] Still, the design of watersoluble and biocompatible singlet oxygen-generating molecules remains a challenge.…”