Journal article
High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (Ln(III) = Pr, Nd, Sm, Eu)
Inorganic chemistry, v 56(21), pp 13152-13165
06 Nov 2017
PMID: 29068667
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Abstract
Complexes {[LnCu(5)(GlyHA)(5)(m-bdc)(H2O)(4x)](2)[LnCu(5)(GlyHA)(5)(SO4)(m-bdc)(H2O)(4)](2)}(30 + 2x)H2O (where GlyHA(2) = glycinehydroxamate, m-bdc(2) = 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)](n)n[NdCu5(GlyHA)(5)(H2O)(4)(mu-CO3)(m-bdc)]}13nH(2)O (2) and {[EuCu5(GlyHA())5(H2O)(3)](m-bdc)(2)[EuCu5(GlyHA)(5)(m-bdc)(H2O)(3)]}n17nH(2)O (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu(5)(GlyHA)(5)(SO4)(H2O)(6.5)]}(2)(SO4)6H(2)O (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 [LnCu(5)(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)(mu-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 cm(3)/g of methanol vapor or 0.04 cm(3)/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 chi T-M vs T data for complexes 14 and their simpler starting materials {[LnCu(5)(GlyHA)(5)(SO4)(H2O)(6.5)]}(2)(SO4)6H(2)O (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(CuCu) < -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.
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Details
- Title
- High Nuclearity Assemblies and One-Dimensional (1D) Coordination Polymers Based on Lanthanide-Copper 15-Metallacrown-5 Complexes (Ln(III) = Pr, Nd, Sm, Eu)
- Creators
- Anna V. Pavlishchuk - Taras Shevchenko National University of KyivSergey V. Kolotilov - L.V. Pisarzhevskii Institute of Physical ChemistryMatthias Zeller - Youngstown State UniversitySamuel E. Lofland - Rowan UniversityLaurence K. Thompson - Memorial University of NewfoundlandAnthony W. Addison - Drexel UniversityAllen D. Hunter - Purdue University West Lafayette
- Publication Details
- Inorganic chemistry, v 56(21), pp 13152-13165
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 14
- Grant note
- 0087210 / NSF; National Science Foundation (NSF) CAP-491 / Ohio Board of Regents National Academy of Sciences of Ukraine Youngstown State University 611488 / European Community's Seventh Framework Programme Fulbright Foundation Drexel University
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000414820100054
- Scopus ID
- 2-s2.0-85033411093
- Other Identifier
- 991019169692504721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear