20 Å Cd4In16S3514- supertetrahedral T4 clusters as building units in decorated cristobalite frameworks
20 Å Cd4In16S3514- supertetrahedral T4 clusters as building units in decorated cristobalite frameworks
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DOI：
10.1021/ja010413f
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发表时间：
2001-05-23
影响因子：
15
通讯作者：
Yaghi, OM
中科院分区：
文献类型：
--
作者：
Li, HL;Kim, J;Yaghi, OM
用一组顶点化装饰取代网络中的顶点的过程已被认为是设计低密度（多孔）金属有机框架的重要策略。我们和其他人最近在基于TX4 （T1）四面体的无机框架合成中采用了这种策略，通过使用n个超四面体簇，其中n个四面体沿着每条边连接，如图1所示。2,3 Ge4S10 -(T2)和In10S20 -和B10S20 -(T3)超四面体连接到SiO2（金刚石网络上的Si原子）的方石骨架中，其中SiO4四面体被T2或T3团簇取代，形成大孔结构。然而，具有更大的Tn超四面体单元的结构仍然未知，尽管它们有潜力创造新的低密度纳米多孔晶体固体，以及产生有序和规则的簇阵列，其大小与cd和其他12族硫属化合物的四面体量子点的单个纳米晶体相当。在这里，我们报道了在cd4in16s3310 -方英石框架中制备20 Å维数6的T4簇，并讨论了Cd2+在促进这种结构实现中的重要作用。以In （65.0 mg, 0.57 mmol）、S （45.0 mg, 1.40 mmol）、Cd (CH3CO2) 2、2H2O （40.0 mg, 0.15 mmol）和1,4 -双（3-氨基丙基）哌嗪（BAPP）为溶剂，以水（1.0 mL）和乙二醇（0.5 mL）溶液混合反应制备Cd4In16S33， （H2O） 20 (C10H28N4) 2.5（以下简称CdInS-44）黄色八面体晶体。
The process of replacing a vertex in a network by a group of vertexesstermed decorationshas been recognized as an important strategy for designing low-density (porous) metal-organic frameworks. 1 We and others have recently employed this strategy in the synthesis of inorganic frameworks based on TX4 (T1) tetrahedra by using Tn supertetrahedral clusters in which n tetrahedra are linked along each edge as illustrated in Figure 1. 2, 3 Ge4S10 4-(T2) and In10S20 10-and B10S20 10-(T3) supertetrahedra have been linked into the cristobalite framework of SiO2 (Si atoms on a diamond network), in which SiO4 tetrahedra are replaced by T2 or T3 clusters to produce large-pore structures. However, structures with larger Tn supertetrahedral units remain unknown, 4 although they have the potential of creating novel low-density nanoporous crystalline solids as well as yielding ordered and regular arrays of clusters that are comparable in size to individual nanocrystallites of tetrahedral quantum dots of CdS and other group 12 chalcogenides. 4, 5 Here we report the preparation of T4 clusters of 20 Å dimension6 in a Cd4In16S33 10-cristobalite framework, and discuss the essential role Cd2+ plays in facilitating the realization of such structures.Yellow octahedral crystals of Cd4In16S33 ‚(H2O) 20 (C10H28N4) 2.5 (hereafter CdInS-44) were prepared by reacting a water (1.0 mL) and ethylene glycol (0.5 mL) solution mixture of In (65.0 mg, 0.57 mmol), S (45.0 mg, 1.40 mmol), Cd (CH3CO2) 2 ‚2H2O (40.0 mg, 0.15 mmol), and 1, 4-bis (3-aminopropyl) piperazine (BAPP)