Two new bimetallic phosphates assembled from the 4-ring building units and influence of metal on the phase selectivity

Two new bimetallic phosphates [(CH3)2NH]0.5[Zn0.62Co0.38PO3OH] (ZnCoPO-CJ48) and [(CH3)2NH2][Zn2.3Mn0.7(PO4)2(PO3OH)]·H3O (ZnMnPO-CJ49) have been solvothermally synthesized in the similar reaction system. ZnCoPO-CJ48 is a layered zinco-cobalt phosphate with neutral framework, its structure is constructed by the connection of Zn(Co)O4 and PO3OH tetrahedra forming a novel 2-D sheet with 3- and 4-rings. The alternating connection of Zn(Mn)O4 and PO4/PO3OH tetrahedra results in the open framework of ZnMnPO-CJ49 with 16-ring extra-large channels. Notably, both compounds are featured by the 4-ring building units T2P2O6(OH)2 formed by the connection of two TO4 tetrahedra and two PO3OH tetrahedra. The 3-D structure of ZnMnPO-CJ49 can be viewed as the connection of zinc–manganese phosphate layers analogous to the layered structure of ZnCoPO-CJ48 by the 1-D edge-sharing 4-ring chains as the pillars. In this work, the synthetic conditions of these two compounds and the influence of metal on the phase selectivity have been discussed in detail.