Synthesis and Alkali Metal Ion Binding Properties of Two Rigid Sterochemical Isomers of Calix[6]arene Bis-crown-4
Cone and 1,2,3-alternate stereochemical isomers of 37,40-diallyloxy-(38,42),(39,41)-bis-crown-4 calix[6]arene, 3 and 4 were isolated in moderate yields by bridging the dialkylated calix[6]arene 2 with triethylene glycol di-p-tosylate. The alkali metal complex stoichiometries, association constants,...
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| Veröffentlicht in: | Journal of the American Chemical Society 2000-02, Vol.122 (7), p.1486-1491 |
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| container_title | Journal of the American Chemical Society |
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| creator | Blanda, Michael T Farmer, Dustin B Brodbelt, Jennifer S Goolsby, Brian J |
| description | Cone and 1,2,3-alternate stereochemical isomers of 37,40-diallyloxy-(38,42),(39,41)-bis-crown-4 calix[6]arene, 3 and 4 were isolated in moderate yields by bridging the dialkylated calix[6]arene 2 with triethylene glycol di-p-tosylate. The alkali metal complex stoichiometries, association constants, and ion selectivities of 3 and 4 were studied by 1H NMR titration experiments, liquid−liquid extraction, electrospray ionization mass spectroscopy, and X-ray crystallography. Good agreement between the gas-phase and solution-phase studies regarding these metal binding properties was observed. Both conformers formed 1:1 complexes with all alkali metal ions but were structurally preorganized such that each exhibited a strong preference for the larger cesium ion as evidenced by the “deep-cavity” cesium complex of host 4, wherein π-metal interactions helped to stabilize the complex. The Cs+/Na+ selectivity factor for 4 was found to be 1500, while that of 3 was only 140. |
| doi_str_mv | 10.1021/ja991810h |
| format | Article |
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The alkali metal complex stoichiometries, association constants, and ion selectivities of 3 and 4 were studied by 1H NMR titration experiments, liquid−liquid extraction, electrospray ionization mass spectroscopy, and X-ray crystallography. Good agreement between the gas-phase and solution-phase studies regarding these metal binding properties was observed. Both conformers formed 1:1 complexes with all alkali metal ions but were structurally preorganized such that each exhibited a strong preference for the larger cesium ion as evidenced by the “deep-cavity” cesium complex of host 4, wherein π-metal interactions helped to stabilize the complex. The Cs+/Na+ selectivity factor for 4 was found to be 1500, while that of 3 was only 140.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja991810h</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2000-02, Vol.122 (7), p.1486-1491</ispartof><rights>Copyright © 2000 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-dc5c009e96c4528365288fdd6e873e2224299f2a405ab16da0f9c38ba2faf6c63</citedby><cites>FETCH-LOGICAL-a361t-dc5c009e96c4528365288fdd6e873e2224299f2a405ab16da0f9c38ba2faf6c63</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja991810h$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja991810h$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids></links><search><creatorcontrib>Blanda, Michael T</creatorcontrib><creatorcontrib>Farmer, Dustin B</creatorcontrib><creatorcontrib>Brodbelt, Jennifer S</creatorcontrib><creatorcontrib>Goolsby, Brian J</creatorcontrib><title>Synthesis and Alkali Metal Ion Binding Properties of Two Rigid Sterochemical Isomers of Calix[6]arene Bis-crown-4</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Cone and 1,2,3-alternate stereochemical isomers of 37,40-diallyloxy-(38,42),(39,41)-bis-crown-4 calix[6]arene, 3 and 4 were isolated in moderate yields by bridging the dialkylated calix[6]arene 2 with triethylene glycol di-p-tosylate. The alkali metal complex stoichiometries, association constants, and ion selectivities of 3 and 4 were studied by 1H NMR titration experiments, liquid−liquid extraction, electrospray ionization mass spectroscopy, and X-ray crystallography. Good agreement between the gas-phase and solution-phase studies regarding these metal binding properties was observed. Both conformers formed 1:1 complexes with all alkali metal ions but were structurally preorganized such that each exhibited a strong preference for the larger cesium ion as evidenced by the “deep-cavity” cesium complex of host 4, wherein π-metal interactions helped to stabilize the complex. The Cs+/Na+ selectivity factor for 4 was found to be 1500, while that of 3 was only 140.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><recordid>eNptkE1PAjEQhhujiYge_Ae9ePCw2nZ3u9sjEkUSiEQwkhjTlG4L5aPFdg3w7y1iOHmZySTPPJN5AbjG6A4jgu_ngjFcYjQ7AQ2cE5TkmNBT0EAIkaQoaXoOLkKYxzEjJW6Ar-HO1jMVTIDCVrC1XIilgX1ViyXsOgsfjK2MncKBd2vla6MCdBqONg6-mqmp4LBW3smZWhm53whupfwv0o6e7Qf9FF5ZFTUhkd5tbJJdgjMtlkFd_fUmeHt6HLWfk95Lp9tu9RKRUlwnlcwlQkwxKrOclCmNpdRVRVVZpIoQkhHGNBEZysUE00ogzWRaTgTRQlNJ0ya4PXjj3RC80nztzUr4HceI77Pix6wimxxYE2q1PYLCLzgt0iLno8GQZ8W4__DeGXMW-ZsDL2Tgc_ftbfzkH-8PMTZ3sA</recordid><startdate>20000223</startdate><enddate>20000223</enddate><creator>Blanda, Michael T</creator><creator>Farmer, Dustin B</creator><creator>Brodbelt, Jennifer S</creator><creator>Goolsby, Brian J</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20000223</creationdate><title>Synthesis and Alkali Metal Ion Binding Properties of Two Rigid Sterochemical Isomers of Calix[6]arene Bis-crown-4</title><author>Blanda, Michael T ; Farmer, Dustin B ; Brodbelt, Jennifer S ; Goolsby, Brian J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a361t-dc5c009e96c4528365288fdd6e873e2224299f2a405ab16da0f9c38ba2faf6c63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Blanda, Michael T</creatorcontrib><creatorcontrib>Farmer, Dustin B</creatorcontrib><creatorcontrib>Brodbelt, Jennifer S</creatorcontrib><creatorcontrib>Goolsby, Brian J</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Blanda, Michael T</au><au>Farmer, Dustin B</au><au>Brodbelt, Jennifer S</au><au>Goolsby, Brian J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Alkali Metal Ion Binding Properties of Two Rigid Sterochemical Isomers of Calix[6]arene Bis-crown-4</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2000-02-23</date><risdate>2000</risdate><volume>122</volume><issue>7</issue><spage>1486</spage><epage>1491</epage><pages>1486-1491</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Cone and 1,2,3-alternate stereochemical isomers of 37,40-diallyloxy-(38,42),(39,41)-bis-crown-4 calix[6]arene, 3 and 4 were isolated in moderate yields by bridging the dialkylated calix[6]arene 2 with triethylene glycol di-p-tosylate. The alkali metal complex stoichiometries, association constants, and ion selectivities of 3 and 4 were studied by 1H NMR titration experiments, liquid−liquid extraction, electrospray ionization mass spectroscopy, and X-ray crystallography. Good agreement between the gas-phase and solution-phase studies regarding these metal binding properties was observed. Both conformers formed 1:1 complexes with all alkali metal ions but were structurally preorganized such that each exhibited a strong preference for the larger cesium ion as evidenced by the “deep-cavity” cesium complex of host 4, wherein π-metal interactions helped to stabilize the complex. The Cs+/Na+ selectivity factor for 4 was found to be 1500, while that of 3 was only 140.</abstract><pub>American Chemical Society</pub><doi>10.1021/ja991810h</doi><tpages>6</tpages></addata></record> |
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| title | Synthesis and Alkali Metal Ion Binding Properties of Two Rigid Sterochemical Isomers of Calix[6]arene Bis-crown-4 |
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