Department of Chemistry, Technical University of Munich, 85748, Garching, Germany.
Computational Materials Chemistry Group, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Bochum, Germany.
Nat Commun. 2019 Oct 29;10(1):4921. doi: 10.1038/s41467-019-12876-1.
The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) - retrofitting - has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@CuBTC (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.
后合成在开放式金属位（OMS）和金属有机骨架（MOF）中配位不足的金属节点之间安装连接分子 - 改造 - 最近被发现是一种操纵宏观性质的强大工具，例如机械鲁棒性和热膨胀行为。到目前为止，用于改造实验的交联剂（CL）的选择是基于定性考虑。在这里，我们提出了一个低成本的计算框架，为实验提供了一种评估各种 CL 用于改造给定 MOF 系统的 OMS 的工具。在将我们的方法应用于原型系统 CL@CuBTC（BTC=1,3,5-苯三甲酸）之后，该方法扩展到 NOTT-100 和 NOTT-101 MOFs，确定了几种有前途的 CL 用于未来的 CL@NOTT-100 和 CL@NOTT-101 改造实验。开发的模型很容易适应其他具有 OMS 的 MOF，并被设置为供实验人员使用，为合成具有改性物理化学性质的新型改造 MOF 提供了指导。
