Inorganic Chemistry II-Organometallics & Material Chemistry, ‡Physical Chemistry I and Laboratory of Industrial Chemistry, and §Inorganic Chemistry I-Bioinorganic Chemistry, Ruhr-University , Universitätsstrasse 150, 44801 Bochum, Germany.
J Am Chem Soc. 2014 Jul 9;136(27):9627-36. doi: 10.1021/ja503218j. Epub 2014 Jun 25.
A series of defect-engineered metal-organic frameworks (DEMOFs) derived from parent microporous MOFs was obtained by systematic doping with defective linkers during synthesis, leading to the simultaneous and controllable modification of coordinatively unsaturated metal sites (CUS) and introduction of functionalized mesopores. These materials were investigated via temperature-dependent adsorption/desorption of CO monitored by FTIR spectroscopy under ultra-high-vacuum conditions. Accurate structural models for the generated point defects at CUS were deduced by matching experimental data with theoretical simulation. The results reveal multivariate diversity of electronic and steric properties at CUS, demonstrating the MOF defect structure modulation at two length scales in a single step to overcome restricted active site specificity and confined coordination space at CUS. Moreover, the DEMOFs exhibit promising modified physical properties, including band gap, magnetism, and porosity, with hierarchical micro/mesopore structures correlated with the nature and the degree of defective linker incorporation into the framework.
通过在合成过程中系统地用缺陷配体掺杂，得到了一系列源自母体微孔 MOF 的缺陷工程化金属有机骨架（DEMOF），从而可以同时且可控地修饰配位不饱和金属位（CUS）并引入功能化介孔。通过在超高真空条件下使用傅里叶变换红外光谱监测 CO 的温度依赖吸附/解吸来研究这些材料。通过将实验数据与理论模拟相匹配，推导出了在 CUS 处生成的点缺陷的精确结构模型。结果表明，CUS 处的电子和空间位阻性质存在多元多样性，证明了在单个步骤中可以在两个尺度上对 MOF 缺陷结构进行调制，以克服 CUS 处活性位特异性受限和配位空间受限。此外，DEMOF 表现出有前景的物理性质的改进，包括带隙、磁性和孔隙率，并且具有与缺陷配体掺入骨架的性质和程度相关的分级微/介孔结构。
