A supramolecular polymer based on ethynyl core-substituted naphthalenediimides reacted with various amines quantitatively without a catalyst, exhibiting unconventional reaction kinetics and products.

Development of atom-economical, catalyst-free, and benign synthetic methods for functionalizing π-conjugated molecules is of great interest for unconventional organic materials. Here, we report catalyst-free 1,6-or more π-extended conjugate addition of amines to ethynyl groups directly attached to various electron-deficient π-systems. This hydroamination proceeded quantitatively under mild conditions to afford amino-functionalized π-systems. A kinetic study of the reaction revealed that the rate-determining step was the nucleophilic attack of an amine to the π-system, and the reaction obeyed typical second-order kinetics. We found that the hydroamination rates of the π-systems (the [a

A nucleation–elongation self-assembling process of a core-substituted naphthalenediimide induced by a catalyst-free amino–yne click reaction at 298 K is reported.