Transformations of a layer and a chain aluminophosphates to the zeotype ∣Al–P–M–O∣–GIS (M = Co2+, Mn2+, Mg2+)

A two-dimensional (2-D) layer aluminophosphate ∣(C2H8N)2∣[Al2(HPO4)(PO4)2] (1) and a 1-D chain aluminophosphate ∣NH3CH2CH2NH3∣[AlP2O8H] (2) have been prepared in the solvothermal system. In the presence of metal M2+ cations (M = Co2+, Mn2+, Mg2+), compounds 1 and 2 transform to the 3-D open frameworks of ∣Al–P–M–O∣–GIS. Single-crystal X-ray diffraction, XRD, TG and compositional analyses show that the structures of ∣Al–P–M–O∣–GIS (M = Co2+, Mn2+, Mg2+) are analogous to zeolite gismondine (zeotype GIS) in which 50% metal sites in the framework are occupied by Co2+, Mn2+ or Mg2+ cations, and protonated dimethylamine cations reside in the 8-ring channels. Interestingly, the edge-sharing 4-ring chain (denoted as AlPO-ESC) featured in compounds 1 and 2 remains in the structures of ∣Al–P–M–O∣–GIS. This study not only provides a potential approach to synthesize complex open frameworks through the reaction of low-dimensional precursors with metal cations, but also further suggests that the AlPO-ESC chain might be a basic building unit for the formation of diverse 3-D open-framework structures.