Amino-Ene Click Reaction of Electron-Deficient π-Conjugated Molecules with Negative Activation Enthalpies.

An amino-ene click reaction is a type of aza-Michael addition reaction that is congruent with click chemistry in terms of its reaction efficiency and rate under mild conditions. The amino-ene click reaction is increasingly recognized as a prominent synthetic tool to form C-N bonds in the context of organic materials chemistry and polymer chemistry. Herein, an unconventional amino-ene click reaction with negative activation enthalpies, in which an electron-deficient π-conjugated molecule, such as a naphthalenediimide, reacts with an amine faster at lower temperatures is reported.

One-step synthesis of perylenediimides exhibiting near-infrared absorption and emission by amino-yne click reaction.

The facile synthesis of chromophores with near-infrared (NIR) absorption and emission is of particular interest due to their wide range of applications. Here we report a one-step synthesis of amino-functionalized perylenediimides exhibiting NIR absorption and emission a catalyst-free amino-yne click reaction. We also demonstrate the post-modification of polyethylenimine by the click reaction, resulting in the formation of a polymeric NIR chromophore with an emission peak at 913 nm in the solid state.

Amino-Functionalization of Vinyl-Substituted Aromatic Diimides by Quantitative and Catalyst-Free Hydroamination*.

Development of facile and versatile synthetic tools for decorating π-conjugated molecules has attracted considerable interest because of their potential application in creating novel functional π-systems. Reported herein are quantitative catalyst-free hydroamination reactions of a series of aromatic diimide compounds having vinyl groups at the π-core, which have been confirmed by NMR, UV-vis absorption spectroscopy, mass analysis, and single-crystal X-ray structural analysis. Kinetic studies revealed that the hydroamination reaction of a vinyl-substituted naphthalenediimide with an aliphatic amine proceeded rapidly under benign conditions.

Immobilization of Ethynyl-π-Extended Electron Acceptors with Amino-Terminated SAMs by Catalyst-Free Click Reaction.

Surface modification of SiO using a catalyst-free quantitative reaction between an amine and an ethynyl-π-extended naphthalenediimide was investigated. A post-reaction method, in which the catalyst-free reaction was performed at the surface after the formation of amino-terminated self-assembled monolayers (SAMs), resulted in dense, uniform modification of the SiO surface with the naphthalenediimide molecules. Both X-ray reflectivity and angle-resolved X-ray photoemission spectroscopy showed consistent results for the layer thickness and density.