NaZnAlP2O8: A New KZnBP2O8‐Type Congruent‐Melting Microporous Zincoaluminophosphate Accessed by Substitution Design Strategy and Molten Salt Method

Abstract A new KZnBP 2 O 8 ‐type open‐frame zincoaluminophosphate, NaZnAlP 2 O 8 (NZAPO), was obtained by a substitution design strategy and synthesized by a high temperature molten salt method. The structure of NZAPO was constructed by [ZnAlP 2 O 8 ] ∞ tetrahedral frame and Na + ions, which is similar to those of KZnBP 2 O 8 (KZBPO). With the remixing of Zn and Al in the new 4×8×8 network, NZAPO was characterized by enlarged eight‐membered loops as compared with those of KZBPO, indicating the high flexibility of [ZnAlP 2 O 8 ] ∞ tetrahedral frame and the validity of substitution design strategy to the access of fascinating open‐frame KZBPO‐type crystals. Remarkably, NZAPO not only exhibited similar optical properties with KZBPO but also featured a fascinating congruent melting behaviour, confirming the superiority of NZAPO in the family of KZBPO‐type crystals.