Assembly of a Heterometallic Cu(II)-Pd(II) Cage by Post-assembly Metal Insertion
Date
2022
Authors
Yong, M.T.
Linder-Patton, O.M.
Bloch, W.M.
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Journal article
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Inorganic Chemistry, 2022; 61(32):12863-12869
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Mei Tieng Yong, Oliver M. Linder-Patton, and Witold M. Bloch
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Abstract
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 CuII metal−organic cage (MOC) that is functionalized with free bis(pyrazolyl)methane sites. The homometallic Cu₄L₄ cage is isolated as a water-stable crystalline solid, and its formation is dependent on metal−ligand stoichiometry and the pre-organization of the Cu₂ paddlewheel. We show by X-ray diffraction and SEM−EDX that PdII chloride can be quantitatively inserted into the free chelating sites of the MOC to yield a [Cu₄(L(PdCl₂))₄] 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.
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© 2022 American Chemical Society