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

Anna V. Pavlishchuk, Sergey V. Kolotilov, Matthias Zeller, Samuel E. Lofland, Laurence K. Thompson, Anthony W. Addison, Allen D. Hunter

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12 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)13152-13165
Number of pages14
JournalInorganic Chemistry
Volume56
Issue number21
DOIs
StatePublished - Nov 6 2017

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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