ACO-Zeotype Iron Aluminum Phosphates with Variable Al/Fe Ratios Controlled by F− Ions

Three new iron aluminum phosphates |(C2H10N2)4|[Fe8 − xAlxFx(H2O)2 − x(PO4)8]·2H2O (χ = 1.64, 1.33, 0.80) with ACO-zeotype structures denoted as FeAPO-CJ66(a), FeAPO-CJ66(b), and FeAPO-CJ66(c), respectively, have been synthesized in the fluoride ion system. Their framework structures are made of double 4-ring (D4R) building units formed by the alternating connection of Fe(Al)O4F(O) trigonal bipyramids and PO4 tetrahedra, which possess 3D intersecting 8-ring channels running along the [001], [010], and [100] directions. Fluoride ions or water molecules reside in the center of D4Rs, and diprotonated ethylenediamine cations and water molecules are occluded in the free space of channels to stabilize the whole structure. Notably, the Al/Fe ratios in the frameworks can be effectively controlled from 1/3.9 to 1/5.0 to 1/9.0 by adjusting the amounts of phosphoric acid and hydrofluoric acid added to the initial reaction mixture. Mössbauer and magnetic measurements show that the Fe ions in the compounds are bivalent and undergo antiferromagnetic ordering at room temperature.