LAUSR

Constructed through relatively weak noncovalent forces, the stability of organic supramolecular materials has shown to be a challenge. Herein, designing of linear conjugated polymer is proposed through creating chain polymer connected via bridging covalent bonds in one direction and retaining π-stacked aromatic columns in its orthogonal direction. Specifically, three analogues of linear conjugated polymers through tuning aromatic core and its covalently linked moiety (bridging group) within the building block monomer were prepared. Cooperatively supported by strong π-π stacking interactions from the extended aromatic core of perylene and favorable dipole-dipole interactions from bridging group, the as-expected high crystallinity, wide light absorption and increased stability was successfully achieved for Oxamide-PDI through ordered molecular arrangement, and presented a remarkable full-spectrum oxygen evolution rate of 5110.25 μmol g-1 h-1 without any cocatalyst. Notably, experimental and theoretical studies revealed that large internal dipole moments within Oxamide-PDI DFT together with its ordered crystalline structure enabled a robust built-in electric field for efficient charge carrier migration and separation. Moreover, DFT calculations also revealed oxidative sites located at carbon atoms next to imide bonds and inner bay positions based on proved spatially separated photogenerated electrons and holes, thus resulting in highly efficient water photolysis into oxygen. This article is protected by copyright. All rights reserved.