Rapid Construction of Double Crystalline Prussian Blue Analogue Hetero‐Superstructure

Abstract The controllable construction of complex metal–organic coordination polymers (CPs) merits untold scientific and technological potential, yet remains a grand challenge of one‐step construction and modulating simultaneously valence states of metals and topological morphology. Here, a thiocyanuric acid (TCA)‐triggered strategy is presented to one‐step rapid synthesis a double‐crystalline Prussian blue analogue hetero‐superstructure (PBA‐hs) that comprises a Co₃[Fe(CN)₆]₂ cube overcoated with a KCo[Fe(CN)₆] shell, followed by eight self‐assembled small cubes on vertices. Unlike common directing surfactants, TCA not only acts as a trigger for the fast growth of KCo[Fe(CN)₆] on the Co₃[Fe(CN)₆]₂ phase resulting in a PBA‐on‐PBA hetero‐superstructure, but also serves as a flange‐like bridge between them. By combining experiments with simulations, a deprotonation‐induced electron transfer (DIET) mechanism is proposed for formation of second phase in PBA‐hs, differing from thermally and photo‐induced electron transfer processes. To prove utility, the calcined PBA‐hs exhibits enhanced oxygen evolution reaction performance. This work provides a new method to design of novel CPs for enriching chemistry and material science. This work offers a practical approach to design novel CPs for enriching chemistry and material science.