Synthesis of Perylene Dyes with Multiple Triphenylamine Substituents

Abstract

Perylene monoimide (PMI) was brominated to give tetra- and tribrominated molecules, which underwent a Suzuki coupling reaction with 4-(diphenylamino)phenylboronic acid to give PMI derivatives. The photophysical and electrochemical properties of the synthesized compounds were investigated, and theoretical calculations were performed. Single crystals of tetrasubstituted PMI were grown and studied in detail. The structure-property relationships were examined to reveal the effect of the position and number of substituents on the perylene core unit. All molecules showed a broad absorption up to 750 nm. Corresponding anhydrides of PMIs were used for fabrication of dye-sensitized solar cells. The molecule with four triphenylamine units on perylene monoanhydride showed the highest power conversion efficiency.

Hexa‐peri‐hexabenzocoronene with Different Acceptor Units for Tuning Optoelectronic Properties

“…It should be noted that these broad bands also overlap with the α‐band of the HBC core, which nevertheless does not extend over 425 nm (Figure A) . In contrast, no red‐shifted absorption band was visible in the absorption spectrum of HBC‐PMI , compared to the absorption of the PMI unit itself, suggesting the absence of the ground‐state CT.…”

“…HBC derivatives have gained great interest as organic functional materials with phase‐forming behavior, serving as donor materials in organic photovoltaics (OPV) as well as p ‐type semiconductors in organic field‐effect transistors (OFETs) . Herein we report syntheses of three HBC–acceptor dyads ( HBC‐A ) bearing different acceptor units, i.e., 9,10‐anthraquinone ( AQ ), naphthalene‐1,8‐dicarboximide ( NMI ), and perylene‐3,4‐dicarboximide ( PMI ) (Figure ). The three HBC–acceptor dyads demonstrate varied photophysical and optoelectronic properties and, depending on the acceptor unit, allowed for a fine control of their optical properties and energy gaps.…”

“…compared to the absorption of the PMI unit itself, [11] suggesting the absence of the ground-state CT.…”

Sensitizers with rigidified-aromatics as the conjugated spacers for dye-sensitized solar cells

“…40 (58) which containing three electron-donating groups by using Sonogashira cross coupling reaction, and achieved the power conversion efficiency of 2.9% after 6 hours of dye-soaking. 47 Both cells had low efficiencies because the larger molecular size diminished the dye concentration on the TiO 2 surface. 47 Both cells had low efficiencies because the larger molecular size diminished the dye concentration on the TiO 2 surface.…”

1,7,9,10‐Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis

“…[34][35] Valiyaveettil andco-worker later reported bromination of PMIs resulting in mixtures of tribromo PMIs (81 %y ield) and 1,6,9,10tetrabromo PMI (13 %y ield) which underwent subsequent Suzuki coupling. [36] Koner et al adopted the idea of using multiple brominated perylenem onoimides (PMI) to introduce different electron-donating groupst ot he perylene scaffold by synthesizing 1,6,9,10-tetrabromoP MI with 46 %y ield followed by nucleophilic aromatic substitutions with different substituted phenolsand thiophenols. [37,38] Although many of these earlier works have demonstrated the potentialo ft he rylene scaffold, some of the procedures use up to 200 equivalents of bromine during the synthesis which could effectively preventa ny possible large-scale applications.T herefore, in the search for novel photoactive materials, the discovery of straightforward synthetic procedures that give the desired photosensitizers in high yields and use more environmentally friendly procedures is essential to be ablet oc reate safe and ecofriendly alternatives to fossil fuels.…”