Transformations of a layer and a chain aluminophosphates to the zeotype {divides}Al-P-M-O{divides}-GIS (M = Co²⁺, Mn²⁺, Mg²⁺)

A two-dimensional (2-D) layer aluminophosphate {divides}(C₂H₈N)₂{divides}[Al₂(HPO₄)(PO₄)₂] (1) and a 1-D chain aluminophosphate {divides}NH₃CH₂CH₂NH₃{divides}[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 {divides}Al-P-M-O{divides}-GIS. Single-crystal X-ray diffraction, XRD, TG and compositional analyses show that the structures of {divides}Al-P-M-O{divides}-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 {divides}Al-P-M-O{divides}-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.