Single-Crystal to Single-Crystal Mechanical Contraction of Metal鈥揙rganic Frameworks through Stereoselective Postsynthetic Bromination

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• 作者：Ross J. Marshall ; Sarah L. Griffin ; Claire Wilson ; Ross S. Forgan
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 5, 2015
• 年：2015
• 卷：137
• 期：30
• 页码：9527-9530
• 全文大小：380K
• ISSN：1520-5126

文摘

The properties of metal鈥搊rganic frameworks (MOFs) can be tuned by postsynthetic modification (PSM) to introduce specific functionalities after their synthesis. Typically, PSM is carried out on pendant functional groups or through metal/ligand exchange, preserving the structure of the MOF. We report herein the bromination of integral alkyne units in a pair of Zr⁴⁺ and Hf⁴⁺ MOFs, which proceeds stereoselectively in a single-crystal to single-crystal manner. The chemical and mechanical changes in the MOFs are extensively characterized, including the crystal structures of the postsynthetically brominated materials, which show a mechanical contraction of up to 3.7% in volume. The combination of stability and chemical reactivity in these MOFs leads to the possibility of tuning mechanical properties by chemical transformation while also opening up new routes to internal pore functionalization.