State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P.R. China.
Inorg Chem. 2012 Jan 2;51(1):225-9. doi: 10.1021/ic201515z. Epub 2011 Dec 7.
Two divalent-metal-containing aluminophosphates, (C(5)H(14)N(2))[Co(2)Al(4)P(6)O(24)] and (C(5)H(14)N(2))[Zn(2)Al(4)P(6)O(24)] (denoted as MAPO-CJ62; M = Co, Zn), have been hydrothermally synthesized by using N-methylpiperazine as the structure directing agent. Their structures are determined by single crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, and thermogravimetric and diffuse reflectance spectroscopy analyses. Both of these two compounds exhibit a new zeolite framework topology. This new zeolite framework contains 1-dimensional 8-ring channels running along the [010] direction. All the metal and P atoms are tetrahedrally coordinated and alternately connected to each other through bridging O atoms. Inductively coupled plasma analysis shows that the molar ratio of M:Al in MAPO-CJ62 is 1:2. The M(2+) ions in MAPO-CJ62 selectively occupy two of the three possible crystallographically distinct positions. A pure aluminophosphate analogue of MAPO-CJ62 without M(2+)-incorporation, denoted as AlPO-CJ62, has not been obtained in our experiment so far. The necessity of introducing M(2+) ions and their ordered distribution in MAPO-CJ62 has been elucidated by analyzing the distortions of Al-centered tetrahedra in the hypothetical framework of AlPO-CJ62.
两种含二价金属的磷酸铝，（C(5)H(14)N(2))[Co(2)Al(4)P(6)O(24)] 和（C(5)H(14)N(2))[Zn(2)Al(4)P(6)O(24)]（表示为 MAPO-CJ62；M = Co，Zn），已通过使用 N-甲基哌嗪作为结构导向剂在水热条件下合成。通过单晶 X 射线衍射确定了它们的结构，并通过粉末 X 射线衍射、电感耦合等离子体和热重及漫反射光谱分析进行了进一步的表征。这两种化合物都表现出一种新的沸石骨架拓扑结构。这种新的沸石骨架包含沿[010]方向延伸的一维 8 元环通道。所有的金属和 P 原子都是四面体配位的，并通过桥连 O 原子交替连接在一起。电感耦合等离子体分析表明，MAPO-CJ62 中的 M:Al 摩尔比为 1:2。MAPO-CJ62 中的 M(2+) 离子选择性地占据三个结晶学上不同位置中的两个。到目前为止，我们的实验还没有得到没有 M(2+)掺入的 MAPO-CJ62 的纯磷酸铝类似物，AlPO-CJ62。通过分析 AlPO-CJ62 的假设骨架中 Al 中心四面体的变形，阐明了引入 M(2+)离子及其在 MAPO-CJ62 中有序分布的必要性。
