Lu Peng, Zhang Yaping, Mayoral Alvaro, Gómez-Hortigüela Luis, Camblor Miguel A
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC), c/Sor Juana Inés de la Cruz 3, 28049 Madrid, Spain.
Dalton Trans. 2020 Jun 7;49(21):7037-7043. doi: 10.1039/d0dt00818d. Epub 2020 May 12.
HPM-7, a germanosilicate synthesized using long imidazolium-based dications with two different linkers, is shown to possess the POS topology, although disorder may exist but it is very difficult to discern. First, three simple ordered polymorphs (POS-A to POS-C) with very similar energies and structural motifs could give rise to intergrowths that would be very difficult to recognize by powder X-ray diffraction, according to DIFFaX simulations. Another four structures (POS-D to POS-G) can be derived from POS by changing the orientation of two single four rings within the structure, possibly providing an additional source of disorder. While 3D EDT strongly suggests that HPM-7 basically possesses the POS-A (i.e. POS) topology, a detailed HR-STEM study demonstrates the rare existence of some disorder compatible with the polymorph POS-D. The general avoidance of polymorphs with very similar structural motifs and comparable energies points to a rather specific structure-direction by the organic dications used.
HPM - 7是一种使用带有两种不同连接基的长咪唑鎓二价阳离子合成的锗硅酸盐,尽管可能存在无序情况但很难辨别,它显示出具有POS拓扑结构。首先,根据DIFFaX模拟,三种具有非常相似能量和结构基序的简单有序多晶型物(POS - A至POS - C)可能会产生共生生长,这通过粉末X射线衍射很难识别。另外四种结构(POS - D至POS - G)可以通过改变结构内两个单四元环的取向从POS衍生而来,这可能提供了额外的无序来源。虽然三维电子衍射断层成像(3D EDT)强烈表明HPM - 7基本具有POS - A(即POS)拓扑结构,但详细的高分辨率扫描透射电子显微镜(HR - STEM)研究表明,存在一些与多晶型物POS - D相容的罕见无序情况。对具有非常相似结构基序和相当能量的多晶型物的普遍规避表明,所使用的有机二价阳离子具有相当特定的结构导向作用。