Improved Syntheses of Halogenated Benzene-1,2,3,4-Tetracarboxylic Diimides.

The preparation of halogenated benzene-1,2,3,4-tetracarboxylic diimide derivatives is challenging because of the possibility of competitive incorrect cyclizations and SAr reactivity. Here, we demonstrate that bypassing traditional cyclic anhydrides and instead directly reacting dihalobenzene-1,2,3,4-tetracarboxylic acids with primary amines in acetic acid solvent successfully provides a range of desirable -diimide products in good yields. Furthermore, we demonstrate that sterically challenging -derivatizations can be readily achieved under microwave reactor conditions.

Modulating Polymerization Thermodynamics of Thiolactones Through Substituent and Heteroatom Incorporation.

A central challenge in the development of next-generation sustainable materials is to design polymers that can easily revert back to their monomeric starting material through chemical recycling to monomer (CRM). An emerging monomer class that displays efficient CRM are thiolactones, which exhibit rapid rates of polymerization and depolymerization. This report details the polymerization thermodynamics for a series of thiolactone monomers through systematic changes to substitution patterns and sulfur heteroatom incorporation.

Redox-Active Heteroacene Chromophores Derived from a Nonlinear Aromatic Diimide.

This work describes a three-step chromatography-free protocol for the synthesis of a novel organic materials building block, dichlorinated mellophanic diimide (MDI), that is shown to undergo nucleophilic substitution with a variety of disubstituted benzenes to yield a series of chromophores. Furthermore, 1,2,4,5-tetrasubstituted benzenes can be used to synthesize tetraimide heteropentacene derivatives endcapped by MDI motifs. The fine-tuning effects of heteroatom identity were investigated by UV-vis and fluorescence spectroscopy, cyclic and differential pulse voltammetries, and density functional theory calculations.