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Keywords = heterometallic Cr-Cu complexes

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13 pages, 2779 KiB  
Article
Structural and Magnetic Properties of the {Cr(pybd)3[Cu(cyclen)]2}(BF4)4 Heteronuclear Complex
by Fabio Santanni, Laura Chelazzi, Lorenzo Sorace, Grigore A. Timco and Roberta Sessoli
Crystals 2023, 13(6), 901; https://doi.org/10.3390/cryst13060901 - 1 Jun 2023
Viewed by 2113
Abstract
Heterotopic ligands containing chemically different binding centers are appealing candidates for obtaining heteronuclear metal complexes. By exploiting this strategy, it is possible to introduce different paramagnetic centers characterized by specific anisotropic magnetic properties that make them distinguishable when weakly magnetically coupled. This molecular [...] Read more.
Heterotopic ligands containing chemically different binding centers are appealing candidates for obtaining heteronuclear metal complexes. By exploiting this strategy, it is possible to introduce different paramagnetic centers characterized by specific anisotropic magnetic properties that make them distinguishable when weakly magnetically coupled. This molecular approach has great potential to yield multi-spin adducts capable of mimicking logical architectures necessary for quantum information processing (QIP), i.e., quantum logic gates. A possible route for including a single-ion magnetic center within a finite-sized heterometallic compound uses the asymmetric (1-pyridyl)-butane-1,3-dione (pybd) ligand reported in the literature for obtaining Cr3+−Cu2+ metallo-cages. To avoid the formation of cages, we adopted the cyclen (1,4,7,10-tetraazacyclododecane) ligand as a “capping” agent for the Cu2+ ions. We report here the structural and magnetic characterization of the unprecedented adduct {Cr(pybd)3[Cu(cyclen)]2}(BF4)4, whose structure is characterized by a central Cr3+ ion in a distorted octahedral coordination environment and two peripheral Cu2+ ions with square-pyramidal coordination geometries. As highlighted by Continuous Wave Electron Paramagnetic Resonance (EPR) spectroscopy and Direct Current (DC) magnetometry measurements, this adduct shows negligible intramolecular magnetic couplings, and it maintains the characteristic EPR signals of Cr3+ and Cu2+ moieties when diluted in frozen solutions. Full article
(This article belongs to the Special Issue The Polyhedral Face of Coordination Chemistry)
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9 pages, 4548 KiB  
Article
[CrIII8NiII6]n+ Heterometallic Coordination Cubes
by Helen M. O’Connor, Sergio Sanz, Aaron J. Scott, Mateusz B. Pitak, Wim T. Klooster, Simon J. Coles, Nicholas F. Chilton, Eric J. L. McInnes, Paul J. Lusby, Høgni Weihe, Stergios Piligkos and Euan K. Brechin
Molecules 2021, 26(3), 757; https://doi.org/10.3390/molecules26030757 - 2 Feb 2021
Cited by 6 | Viewed by 3826
Abstract
Three new heterometallic [CrIII8NiII6] coordination cubes of formulae [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7 [...] Read more.
Three new heterometallic [CrIII8NiII6] coordination cubes of formulae [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm−1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)–(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd. Full article
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