Single-Crystal to Single-Crystal Mechanical Contraction of Metal–Organic Frameworks through Stereoselective Postsynthetic Bromination
The properties of metal–organic 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...
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| Veröffentlicht in: | Journal of the American Chemical Society 2015-08, Vol.137 (30), p.9527-9530 |
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| container_title | Journal of the American Chemical Society |
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| creator | Marshall, Ross J Griffin, Sarah L Wilson, Claire Forgan, Ross S |
| description | The properties of metal–organic 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. |
| doi_str_mv | 10.1021/jacs.5b05434 |
| format | Article |
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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.</description><subject>Crystallization</subject><subject>Hafnium - chemistry</subject><subject>Halogenation</subject><subject>Hydrocarbons, Brominated - chemical synthesis</subject><subject>Hydrocarbons, Brominated - chemistry</subject><subject>Molecular Structure</subject><subject>Organometallic Compounds - chemistry</subject><subject>Stereoisomerism</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>N~.</sourceid><sourceid>EIF</sourceid><recordid>eNptkLFOwzAURS0EoqWwMaOMDKQ8O7GTjFBRQCoqUmGOXMdpUpK42A6oGxsfwB_yJThqAQkxWLbfO_f6-SJ0jGGIgeDzJRdmSOdAwyDcQX1MCfgUE7aL-gBA_ChmQQ8dGLN015DEeB_1CMMRDXDUR--zsllU0h_ptbG88qzy_lTupCh4Uwp3HKnGai5sqRpP5a7j-p9vH1O96ABvrHktX5V-Mp4ttGoXhTezUktlZCWd6kV698pYs25sIa0TXGpVlw3v_A7RXs4rI4-2-wA9jq8eRjf-ZHp9O7qY-NyNbn2RED4nOacgqFuCAQQ4YNE8pxlLcBZzKrjIcgYxC8M8iDFlmAMNskiyGMJggE43viutnltpbFqXRsiq4o1UrUlxBATiBJIOPdugQitjtMzTlS5rrtcphrSLPu2iT7fRO_xk69zOa5n9wN9Z_z7dqZaq1Y376P9eX7ZBkFI</recordid><startdate>20150805</startdate><enddate>20150805</enddate><creator>Marshall, Ross J</creator><creator>Griffin, Sarah L</creator><creator>Wilson, Claire</creator><creator>Forgan, Ross S</creator><general>American Chemical Society</general><scope>N~.</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20150805</creationdate><title>Single-Crystal to Single-Crystal Mechanical Contraction of Metal–Organic Frameworks through Stereoselective Postsynthetic Bromination</title><author>Marshall, Ross J ; Griffin, Sarah L ; Wilson, Claire ; Forgan, Ross S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a428t-c92ab2fa50c550cc60031367bf5d691d8a5cacdf608644f381561a053d7e68043</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Crystallization</topic><topic>Hafnium - chemistry</topic><topic>Halogenation</topic><topic>Hydrocarbons, Brominated - chemical synthesis</topic><topic>Hydrocarbons, Brominated - chemistry</topic><topic>Molecular Structure</topic><topic>Organometallic Compounds - chemistry</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Marshall, Ross J</creatorcontrib><creatorcontrib>Griffin, Sarah L</creatorcontrib><creatorcontrib>Wilson, Claire</creatorcontrib><creatorcontrib>Forgan, Ross S</creatorcontrib><collection>American Chemical Society Open Access</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Marshall, Ross J</au><au>Griffin, Sarah L</au><au>Wilson, Claire</au><au>Forgan, Ross S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Single-Crystal to Single-Crystal Mechanical Contraction of Metal–Organic Frameworks through Stereoselective Postsynthetic Bromination</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2015-08-05</date><risdate>2015</risdate><volume>137</volume><issue>30</issue><spage>9527</spage><epage>9530</epage><pages>9527-9530</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The properties of metal–organic 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. 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| ispartof | Journal of the American Chemical Society, 2015-08, Vol.137 (30), p.9527-9530 |
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| language | eng |
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| source | MEDLINE; ACS Journals: American Chemical Society Web Editions |
| subjects | Crystallization Hafnium - chemistry Halogenation Hydrocarbons, Brominated - chemical synthesis Hydrocarbons, Brominated - chemistry Molecular Structure Organometallic Compounds - chemistry Stereoisomerism |
| title | Single-Crystal to Single-Crystal Mechanical Contraction of Metal–Organic Frameworks through Stereoselective Postsynthetic Bromination |
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