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High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu).
Inorg Chem. 2017 Nov 06; 56(21):13152-13165.IC

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 χMT 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 < JCu-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.

Authors+Show Affiliations

Department of Chemistry, Taras Shevchenko National University of Kyiv , Volodymyrska str. 62, Kiev 01601, Ukraine. L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine , Prospect Nauki 31, Kiev 03028, Ukraine.L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine , Prospect Nauki 31, Kiev 03028, Ukraine.STaRBURSTT CyberInstrumentation Consortium and Department of Chemistry, Youngstown State University , One University Plaza, Youngstown, Ohio 44555-3663, United States. Department of Chemistry, Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907-2084, United States.Department of Physics and Astronomy, Rowan University , Glassboro, New Jersey 08028, United States.Department of Chemistry, Memorial University , St. John's, Newfoundland, A1B 3X7, Canada.Department of Chemistry, Drexel University , Philadelphia, Pennsylvania 19104-2816, United States.STaRBURSTT CyberInstrumentation Consortium and Department of Chemistry, Youngstown State University , One University Plaza, Youngstown, Ohio 44555-3663, United States. Department of Chemistry, Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907-2084, United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

29068667

Citation

Pavlishchuk, Anna V., et al. "High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based On Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu)." Inorganic Chemistry, vol. 56, no. 21, 2017, pp. 13152-13165.
Pavlishchuk AV, Kolotilov SV, Zeller M, et al. High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu). Inorg Chem. 2017;56(21):13152-13165.
Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Lofland, S. E., Thompson, L. K., Addison, A. W., & Hunter, A. D. (2017). High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu). Inorganic Chemistry, 56(21), 13152-13165. https://doi.org/10.1021/acs.inorgchem.7b01944
Pavlishchuk AV, et al. High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based On Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu). Inorg Chem. 2017 Nov 6;56(21):13152-13165. PubMed PMID: 29068667.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (LnIII = Pr, Nd, Sm, Eu). AU - Pavlishchuk,Anna V, AU - Kolotilov,Sergey V, AU - Zeller,Matthias, AU - Lofland,Samuel E, AU - Thompson,Laurence K, AU - Addison,Anthony W, AU - Hunter,Allen D, PY - 2017/10/27/pubmed PY - 2017/10/27/medline PY - 2017/10/26/entrez SP - 13152 EP - 13165 JF - Inorganic chemistry JO - Inorg Chem VL - 56 IS - 21 N2 - 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 χMT 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 < JCu-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. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/29068667/High_Nuclearity_Assemblies_and_One_Dimensional__1D__Coordination_Polymers_Based_on_Lanthanide_Copper_15_Metallacrown_5_Complexes__LnIII_=_Pr_Nd_Sm_Eu__ L2 - https://dx.doi.org/10.1021/acs.inorgchem.7b01944 DB - PRIME DP - Unbound Medicine ER -
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