Synthesis of sterically congested unsymmetrical 1,2-dicarbonyl radicals through a stepwise approach.

A simplified and stepwise synthetic method for producing sterically congested unsymmetrical 1,2-dicarbonyl radicals was successfully demonstrated including detailed characterization of each radical cation. Using this approach, an aryl- and N-heterocyclic carbene-substituted 1,2-dicarbonyl radical in its neutral form is generated, revealing the stabilizing role of N-heterocyclic carbenes.

Controlling π-π Interactions of Highly Soluble Naphthalene Diimide Derivatives for Neutral pH Aqueous Redox Flow Batteries.

Organic redox-active molecules are a promising platform for designing sustainable, cheap, and safe charge carriers for redox flow batteries. However, radical formation during the electron-transfer process causes severe side reactions and reduces cyclability. This problem is mitigated by using naphthalene diimide (NDI) molecules and regulating their π-π interactions. The long-range π-stacking of NDI molecules, which leads to precipitation, is disrupted by tethering four ammonium functionalities, and the solubility approaches 1.5 m in water. The gentle π-π interactions induce clustering and disassembling of the NDI molecules during the two-electron transfer processes. When the radical anion forms, the antiferromagnetic coupling develops tetramer and dimer and nullifies the radical character. In addition, short-range-order NDI clusters at 1 m concentration are not precipitated but inhibit crossover. They are disassembled in the subsequent electron-transfer process, and the negatively charged NDI core strongly interacts with ammonium groups. These behaviors afford excellent RFB performance, demonstrating 98% capacity retention for 500 cycles at 25 mA cm-2 and 99.5% Coulombic efficiency with 2 m electron storage capacity.