The crystalline chiral zirconium phosphonates with α, γ-type structure, formulated as Zr(PO 4) 0.6(HPO 4) 0.1(O 3PCH 2NHC 4H 7COO-) 0.55(O 3PCH 2NHC 3H 7COOH) 0.55F 0.55·H 2O(mix-ZrPMP, [α] 25 D=-36°) and Zr(PO 4) 0.6(HPO 4) 0.1(O 3PCH 2NHCH 2SC 2H 3COO-) 0.55(O 3PCH 2NHCH 2S-C 2H 3COOH) 0.55F 0.55·2.0H 2O(mix-ZrPMT, [α] 25 D=-39°), were obtained in situ by reaction of N-phosphonomethyl-L-proline(H 3PMP) and N-phosphonomethyl-1,3-thiazolidine-4-carboxylic acid(H 3PMTA) with ZrOCl 2·8H 2O in the presence of HF at 90 ℃, respectively. The heterocycle thiazolidine was integrated onto metal-organic frameworks. Of mix-ZrPMP and mix-ZrPMT, the CO 2H, CO- 2 and NH+ groups are remained in layered structures of mixed-type.
