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

In this work, we present a new synthetic strategy for fourfold‐substituted perylene monoimides via tetrabrominated perylene monoanhydrides. X‐ray diffraction analysis unveiled the intramolecular stacking orientation between the substituents and semicircular packing behavior. We observed the remarkable influence of the substituent on the longevity and nature of the excited state upon visible light excitation. In the presence of poly(dehydroalanine)‐graft‐poly(ethylene glycol) graft copolymers as solubilizing template, the chromophores are capable of sensitizing [Mo3S13]2− clusters in aqueous solution for stable visible light driven hydrogen evolution over three days. Design and use of perylene monoimide dyes: Novel perylene monoimide dyes have been synthesized, and their properties characterized by XRD, spectroscopic and electrochemical methods. A custom‐made photoreactor was used to exhibit light‐driven hydrogen‐evolution catalysis in the presence of (NH4)2[Mo3S13] catalyst and poly(dehydroalanine)‐graft‐poly(ethylene glycol) solubilizing template for the organic photosensitizers.