Uncovering Two Principles of Multivariate Hierarchical Metal-Organic Framework Synthesis via Retrosynthetic Design
Uncovering Two Principles of Multivariate Hierarchical Metal-Organic Framework Synthesis via Retrosynthetic Design
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DOI：
10.1021/acscentsci.8b00722
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发表时间：
2018-12-26
影响因子：
18.2
通讯作者：
Zhou, Hong-Cai
中科院分区：
文献类型：
--
作者：
Feng, Liang;Yuan, Shuai;Zhou, Hong-Cai
多变量（MTV）分级金属有机框架（MOFs），其中包含有序结构排列的多个区域，显示出应用前景，如气体分离，尺寸选择性催化，和控制药物输送。然而，这些分层MOF的复杂性受到框架组装期间缺乏控制的限制。在此，我们报告了两个设计原则，表面功能化和逆合成技术的稳定性控制的指导下，分层的MOF上的MOF结构形成的控制生成。因此，在这些分级系统中实现了空间分布、组成和晶体尺寸的可调谐性。所得的M0 F-on-M0 F分级结构代表独特的结晶多孔材料，其含有在骨架复合材料内结合在一起的官能团和金属簇的可控分布。这种通用的合成方法不仅将传统MTV策略的范围和可调性扩展到多组分材料，而且还提供了一种简便的途径来将变体和序列引入复杂的三维分层和协作系统。作为概念证明，利用卟啉核-MOF的光热效应来触发具有高客体容量的壳-MOF的受控客体释放，突出了多元分级系统中的集成合作行为。
Multivariate (MTV) hierarchical metal-organic frameworks (MOFs), which contain multiple regions arranged in ordered structures, show promise for applications such as gas separation, size-selective catalysis, and controlled drug delivery. However, the complexity of these hierarchical MOFs is limited by a lack of control during framework assembly. Herein, we report the controlled generation of hierarchical MOF-on-MOF structural formation under the guidance of two design principles, surface functionalization and retrosynthetic techniques for stability control. Accordingly, the tunability of spatial distributions, compositions, and crystal sizes has been achieved in these hierarchical systems. The resulting MOF-on-MOF hierarchical structures represent a unique crystalline porous material which contains a controllable distribution of functional groups and metal clusters that are associated together within a framework composite. This general synthetic approach not only expands the scope and tunability of the traditional MTV strategy to multicomponent materials, but also offers a facile route to introduce variants and sequences to sophisticated three-dimensional hierarchical and cooperative systems. As a proof of concept, the photothermal effects of a porphyrinic core-MOF are exploited to trigger the controlled guest release from a shell-MOF with high guest capacity, highlighting the integrated cooperative behaviors in multivariate hierarchical systems.