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

doi:10.1021/acs.inorgchem.7b01944

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

Inorg Chem. 2017 Nov 6;56(21):13152-13165. doi: 10.1021/acs.inorgchem.7b01944.

Authors

Anna V Pavlishchuk^{1

2}, Sergey V Kolotilov², Matthias Zeller^{3

4}, Samuel E Lofland⁵, Laurence K Thompson⁶, Anthony W Addison⁷, Allen D Hunter^{3

4}

Affiliations

¹ Department of Chemistry, Taras Shevchenko National University of Kyiv , Volodymyrska str. 62, Kiev 01601, Ukraine.
² L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine , Prospect Nauki 31, Kiev 03028, Ukraine.
³ STaRBURSTT CyberInstrumentation Consortium and Department of Chemistry, Youngstown State University , One University Plaza, Youngstown, Ohio 44555-3663, United States.
⁴ Department of Chemistry, Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907-2084, United States.
⁵ Department of Physics and Astronomy, Rowan University , Glassboro, New Jersey 08028, United States.
⁶ Department of Chemistry, Memorial University , St. John's, Newfoundland, A1B 3X7, Canada.
⁷ Department of Chemistry, Drexel University , Philadelphia, Pennsylvania 19104-2816, United States.

PMID: 29068667
DOI: 10.1021/acs.inorgchem.7b01944

Abstract

Complexes {[LnCu₅(GlyHA)₅(m-bdc)(H₂O)_4-x]₂[LnCu₅(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)]_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 χ_MT 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.