An open-frame aluminophosphate, K[(Zn 0.5 Al 0.5 ) 2 P 2 O 8 ] (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[ZnBP 2 O 8 ], 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 4 ) 6− and (AlO 4 ) 5− 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.
A new polycation-type phosphate of H{[Na-(H 2 O) 3 ] 6 F}(PO 4 ) 2 • 2(H 2 O) (FNPO) was synthesized by a mild hydrothermal method. FNPO crystallizes in the cubic space group of Fd � 3c with cell parameters of a = 27.778 Å and Z = 32. In the structure of FNPO, every sodium ion is six-fold coordinated to five water molecules and one fluoride ion in forming electroneutral [NaF(H 2 O) 5 ] octahedra, while one kind of super octahedral polycation-type {[Na(H 2 O) 3 ] 6 F} 5 + complexes with center anion of Fis constructed by six [NaF(H 2 O) 5 ] octahedra via the sharing of their terminal fluoride ion and water molecules. Besides counter cation of {[Na(H 2 O) 3 ] 6 F} 5 + complexes, all the other (PO 4 ) 3À and water molecules are in a discrete arrangement with sole connection of hydrogen-bond interaction with {[Na-(H 2 O) 3 ] 6 F} 5 + complexes in forming [101]-oriented pseudo-lines, while each line is hydrogen-bonded to six adjacent lines in generating the three-dimensional structure of FNPO. Benefitted by this polycation-type structure, FNPO was characterized by a deep ultraviolet transparency.
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