High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)

High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)

Complexes {[LnCu5(GlyHA)5(m-bdc)­(H2O)4–x ]2[LnCu5(GlyHA)5(SO4)­(m-bdc)­(H2O)4]2}·(30 + 2x)­H2O (where GlyHA2– = glycinehydroxamate, m-bdc2– = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu5(GlyHA)5(H2O)5(m-bdc)]...

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Veröffentlicht in:Inorganic chemistry 2017-11, Vol.56 (21), p.13152-13165
Hauptverfasser: Pavlishchuk, Anna V, Kolotilov, Sergey V, Zeller, Matthias, Lofland, Samuel E, Thompson, Laurence K, Addison, Anthony W, Hunter, Allen D
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container_issue 21
container_start_page 13152
container_title Inorganic chemistry
container_volume 56
creator Pavlishchuk, Anna V
Kolotilov, Sergey V
Zeller, Matthias
Lofland, Samuel E
Thompson, Laurence K
Addison, Anthony W
Hunter, Allen D
description Complexes {[LnCu5(GlyHA)5(m-bdc)­(H2O)4–x ]2[LnCu5(GlyHA)5(SO4)­(m-bdc)­(H2O)4]2}·(30 + 2x)­H2O (where GlyHA2– = glycinehydroxamate, m-bdc2– = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu5(GlyHA)5(H2O)5(m-bdc)] nn[NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}·13nH2O (2) and {[EuCu5(GlyHA)5(H2O)3]­(m-bdc)2[EuCu5(GlyHA)5(m-bdc)­(H2O)3]} n ·17nH2O (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m-phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu5(GlyHA)5]3+ cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu5(GlyHA)5(H2O)5(m-bdc)]+} n 1D chains in 2 being separated by discrete [NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}− complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm3/g of methanol vapor or 0.04 cm3/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible “gate opening” mechanism upon interaction with this substrate. The χM T vs T data for complexes 1–4 and their simpler starting materials {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln­(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide­(III) and copper­(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu­(II) ions in metallacrown fragments were found to fall in the range of −47 < J Cu–Cu < −63 cm–1. These complexes are the first examples of a Ln­(III)-Cu­(II) 15-metallacrowns-5 (Ln­(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.
doi_str_mv 10.1021/acs.inorgchem.7b01944
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Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu5(GlyHA)5]3+ cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu5(GlyHA)5(H2O)5(m-bdc)]+} n 1D chains in 2 being separated by discrete [NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}− complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm3/g of methanol vapor or 0.04 cm3/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible “gate opening” mechanism upon interaction with this substrate. The χM T vs T data for complexes 1–4 and their simpler starting materials {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln­(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide­(III) and copper­(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu­(II) ions in metallacrown fragments were found to fall in the range of −47 &lt; J Cu–Cu &lt; −63 cm–1. These complexes are the first examples of a Ln­(III)-Cu­(II) 15-metallacrowns-5 (Ln­(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.7b01944</identifier><identifier>PMID: 29068667</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Inorganic chemistry, 2017-11, Vol.56 (21), p.13152-13165</ispartof><rights>Copyright © 2017 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a351t-f466be2f128b44d8895927022191bbcc37a5cb6fa7ed4ea6bcd55bf07c18b6b33</citedby><cites>FETCH-LOGICAL-a351t-f466be2f128b44d8895927022191bbcc37a5cb6fa7ed4ea6bcd55bf07c18b6b33</cites><orcidid>0000-0001-9096-0782 ; 0000-0002-0706-7377</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.7b01944$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.7b01944$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,2766,27078,27926,27927,56740,56790</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29068667$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Pavlishchuk, Anna V</creatorcontrib><creatorcontrib>Kolotilov, Sergey V</creatorcontrib><creatorcontrib>Zeller, Matthias</creatorcontrib><creatorcontrib>Lofland, Samuel E</creatorcontrib><creatorcontrib>Thompson, Laurence K</creatorcontrib><creatorcontrib>Addison, Anthony W</creatorcontrib><creatorcontrib>Hunter, Allen D</creatorcontrib><title>High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Complexes {[LnCu5(GlyHA)5(m-bdc)­(H2O)4–x ]2[LnCu5(GlyHA)5(SO4)­(m-bdc)­(H2O)4]2}·(30 + 2x)­H2O (where GlyHA2– = glycinehydroxamate, m-bdc2– = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu5(GlyHA)5(H2O)5(m-bdc)] nn[NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}·13nH2O (2) and {[EuCu5(GlyHA)5(H2O)3]­(m-bdc)2[EuCu5(GlyHA)5(m-bdc)­(H2O)3]} n ·17nH2O (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m-phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu5(GlyHA)5]3+ cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu5(GlyHA)5(H2O)5(m-bdc)]+} n 1D chains in 2 being separated by discrete [NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}− complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm3/g of methanol vapor or 0.04 cm3/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible “gate opening” mechanism upon interaction with this substrate. The χM T vs T data for complexes 1–4 and their simpler starting materials {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln­(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide­(III) and copper­(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu­(II) ions in metallacrown fragments were found to fall in the range of −47 &lt; J Cu–Cu &lt; −63 cm–1. These complexes are the first examples of a Ln­(III)-Cu­(II) 15-metallacrowns-5 (Ln­(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqFkc9u1DAQxi0EokvhEUA-bqXNYiexkxw4lG2hKy1tJUDiFvnPpOsqtoOdCPbWV0Ccebk-Ca526ZXTjEbf983YP4ReU7KkJKdvhYpL43y4UVuwy0oS2pTlEzSjLCcZo-TbUzQjJPWU8-YIvYjxlhDSFCV_jo7yhvCa82qG_lyYmy2-nFQPIphxh09jBCt7AxELp_GVg-zMWHDReCd6PKdnJ3jlfdDGiTHN8LXvdxZCxO9FBI3TZCPcuBXOaLi_-73ywwABU5Z9glH0vVDB_3D3d79YirFDDz_TpvnGrddr_A5fhwW-1Av82S7w-XTyEj3rRB_h1aEeo68fzr-sLrLN1cf16nSTiYLRMetKziXkHc1rWZa6rhvW5BXJc9pQKZUqKsGU5J2oQJcguFSaMdmRStFaclkUx2i-zx2C_z5BHFtrooJ0rQM_xZY2jJO6YpwmKdtL0ztiDNC1QzBWhF1LSftApk1k2kcy7YFM8r05rJikBf3o-ociCehe8OC_9VNI3x3_E_oXDg-gKQ</recordid><startdate>20171106</startdate><enddate>20171106</enddate><creator>Pavlishchuk, Anna V</creator><creator>Kolotilov, Sergey V</creator><creator>Zeller, Matthias</creator><creator>Lofland, Samuel E</creator><creator>Thompson, Laurence K</creator><creator>Addison, Anthony W</creator><creator>Hunter, Allen D</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9096-0782</orcidid><orcidid>https://orcid.org/0000-0002-0706-7377</orcidid></search><sort><creationdate>20171106</creationdate><title>High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)</title><author>Pavlishchuk, Anna V ; Kolotilov, Sergey V ; Zeller, Matthias ; Lofland, Samuel E ; Thompson, Laurence K ; Addison, Anthony W ; Hunter, Allen D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a351t-f466be2f128b44d8895927022191bbcc37a5cb6fa7ed4ea6bcd55bf07c18b6b33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Pavlishchuk, Anna V</creatorcontrib><creatorcontrib>Kolotilov, Sergey V</creatorcontrib><creatorcontrib>Zeller, Matthias</creatorcontrib><creatorcontrib>Lofland, Samuel E</creatorcontrib><creatorcontrib>Thompson, Laurence K</creatorcontrib><creatorcontrib>Addison, Anthony W</creatorcontrib><creatorcontrib>Hunter, Allen D</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Pavlishchuk, Anna V</au><au>Kolotilov, Sergey V</au><au>Zeller, Matthias</au><au>Lofland, Samuel E</au><au>Thompson, Laurence K</au><au>Addison, Anthony W</au><au>Hunter, Allen D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2017-11-06</date><risdate>2017</risdate><volume>56</volume><issue>21</issue><spage>13152</spage><epage>13165</epage><pages>13152-13165</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Complexes {[LnCu5(GlyHA)5(m-bdc)­(H2O)4–x ]2[LnCu5(GlyHA)5(SO4)­(m-bdc)­(H2O)4]2}·(30 + 2x)­H2O (where GlyHA2– = glycinehydroxamate, m-bdc2– = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu5(GlyHA)5(H2O)5(m-bdc)] nn[NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}·13nH2O (2) and {[EuCu5(GlyHA)5(H2O)3]­(m-bdc)2[EuCu5(GlyHA)5(m-bdc)­(H2O)3]} n ·17nH2O (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m-phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu5(GlyHA)5]3+ cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu5(GlyHA)5(H2O)5(m-bdc)]+} n 1D chains in 2 being separated by discrete [NdCu5(GlyHA)5(H2O)4(μ-CO3)­(m-bdc)]}− complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm3/g of methanol vapor or 0.04 cm3/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible “gate opening” mechanism upon interaction with this substrate. The χM T vs T data for complexes 1–4 and their simpler starting materials {[LnCu5(GlyHA)5(SO4)­(H2O)6.5]}2(SO4)·6H2O (Ln­(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide­(III) and copper­(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu­(II) ions in metallacrown fragments were found to fall in the range of −47 &lt; J Cu–Cu &lt; −63 cm–1. These complexes are the first examples of a Ln­(III)-Cu­(II) 15-metallacrowns-5 (Ln­(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>29068667</pmid><doi>10.1021/acs.inorgchem.7b01944</doi><tpages>14</tpages><orcidid>https://orcid.org/0000-0001-9096-0782</orcidid><orcidid>https://orcid.org/0000-0002-0706-7377</orcidid></addata></record>
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title High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide–Copper 15-Metallacrown‑5 Complexes (LnIII = Pr, Nd, Sm, Eu)
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