From K[ZnBPO] to K[(ZnAl)PO]: Substitution-Induced Microporous Zincoaluminophosphate with a Congruent-Melting Behavior.

An open-frame aluminophosphate, K[(ZnAl)PO] (KZAPO), was rationally designed by a substitution design strategy and synthesized by a high-temperature molten salt method. Compared with the parent crystal of K[ZnBPO], KZAPO was characterized by similar 4 × 8 × 8 networks, a comparable short-wave ultraviolet transparency and a more regular tetrahedral frame with the mixing of (ZnO) and (AlO) anionic groups, highlighting the multifunctional roles that anionic group mixing played in structural and property modulations. In particular, KZAPO was characterized by a high thermal stability (over 850 °C) and a congruent-melting behavior, being conducive to practical applications.