Journal article
Magnetic Properties of Ln(III)-Cu-II 15-Metallacrown-5 Dimers with Terephthalate (Ln(III) = Pr, Nd, Sm, Eu)
European journal of inorganic chemistry, (30), pp 3504-3511
15 Aug 2018
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Abstract
Metathesis of the isomorphous 15-metallacrown-5 complexes {[LnCu(5)(GlyHA)(5)(SO4)(H2O)(6.5)]}(2)(SO4)6H(2)O (Ln(III) = Pr, Nd, Sm, Eu; GlyHA(2-) = glycinehydroxamate) with excess p-bdc(2-) (p-bdc(2-) = terephthalate) gave pairs of isomorphous complexes {[LnCu(5)(GlyHA)(5)(CO3)(H2O)(4)](2)(p-bdc)}15H(2)O [Ln = Pr (1) and Nd (2)] and {[LnCu(5)(GlyHA)(5)(SO4)(H2O)(x)](2)(p-bdc)}yH(2)O [Sm (3) x = 5, y = 12; Eu (4), x = 4, y = 14] as outcomes of partial sulfate replacement. Complexes 1-4 are discrete dimers with two 15-metallacrown-5 blocks {LnCu(5)}(3+), a bridging p-bdc(2-) and a bidentate capping anion on each Ln(3+). The anion caps in 1 and 2 are carbonates from atmospheric CO2 capture, while in 3 and 4 the anion caps are sulfates. Between 3 K and 300 K, intrametallacycle antiferromagnetic exchange interactions amongst the Cu2+ dominate the magnetic properties of 1-4, while for the Ln(3+), spin-orbit coupling and crystal field effects are significant, the former being greater for Sm3+ and Eu3+. The experimental T-M vs. T data were fitted with an additive model reflecting the dominance of the CuCu superexchange, while Ln(3+)Cu(2+) exchange interactions were taken into account through a molecular field approach. The best-fit values (-2J(Cu-Cu)) for the intercopper superexchange interactions range from 88 to 120 cm(-1); the g-factors, spin-orbit coupling () and axial crystal field splitting () parameter values are typical for Ln(III).
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Details
- Title
- Magnetic Properties of Ln(III)-Cu-II 15-Metallacrown-5 Dimers with Terephthalate (Ln(III) = Pr, Nd, Sm, Eu)
- Creators
- Anna V. Pavlishchuk - L.V. Pisarzhevskii Institute of Physical ChemistrySergey V. Kolotilov - L.V. Pisarzhevskii Institute of Physical ChemistryMatthias Zeller - Purdue University West LafayetteSamuel E. Lofland - Rowan UniversityAnthony W. Addison - Drexel University
- Publication Details
- European journal of inorganic chemistry, (30), pp 3504-3511
- Publisher
- Wiley
- Number of pages
- 8
- Grant note
- 90343 / Foundation Volkswagen Stiftung CAP-491 / Ohio Board of Regents Grant National Academy of Sciences of Ukraine Youngstown State University Fulbright Foundation Illinois State University CHE 0087210; CHE 1039689 / National Science Foundation (NSF) Drexel University
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000441549200007
- Scopus ID
- 2-s2.0-85051481156
- Other Identifier
- 991019168493204721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear