Yong Mei Tieng, Linder-Patton Oliver M, Bloch Witold M
Department of Chemistry, The University of Adelaide, Adelaide, South Australia 5005, Australia.
Institute for Nanoscale Science and Technology, College of Science and Engineering, Flinders University, Adelaide, South Australia 5042, Australia.
Inorg Chem. 2022 Aug 15;61(32):12863-12869. doi: 10.1021/acs.inorgchem.2c02046. Epub 2022 Aug 3.
Porous structures based on multi-metallic motifs are receiving growing interest, but their general preparation still remains a challenge. Here, we report the self-assembly and structure of a Cu metal-organic cage (MOC) that is functionalized with free bis(pyrazolyl)methane sites. The homometallic CuL cage is isolated as a water-stable crystalline solid, and its formation is dependent on metal-ligand stoichiometry and the pre-organization of the Cu paddlewheel. We show by X-ray diffraction and SEM-EDX that Pd chloride can be quantitatively inserted into the free chelating sites of the MOC to yield a [Cu(L(PdCl))] structure. Moreover, the solvent employed in the metalation dictates the solid-state isomerism of the heterometallic cage─a further handle to control the MOC's structural diversity and permanent porosity.
基于多金属基序的多孔结构正受到越来越多的关注，但其常规制备仍然是一个挑战。在此，我们报告了一种用游离双（吡唑基）甲烷位点功能化的铜金属有机笼（MOC）的自组装及其结构。同金属CuL笼作为一种水稳定的晶体固体被分离出来，其形成取决于金属-配体化学计量比和铜桨轮的预组装。我们通过X射线衍射和扫描电子显微镜-能谱分析表明，氯化钯可以定量插入到MOC的游离螯合位点中，从而生成[Cu(L(PdCl))]结构。此外，金属化过程中使用的溶剂决定了异金属笼的固态异构现象——这是控制MOC结构多样性和永久孔隙率的另一种手段。
