Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes

Athanasopoulou, Angeliki A.; Carrella, Luca M.; Rentschler, Eva

doi:10.3390/inorganics6030066

Cited by 9 publications

(8 citation statements)

References 51 publications

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“…As with crown ethers, they are characterized by the presence of an oxygen rich core cavity, which may encapsulate guest species. ,, Due to their capacity to bind cations of almost any groupalkali, alkaline earth and transition metals, lanthanides, and main group metals and metalloidsas well as anions or neutral molecules, they have been recognized to be relevant compounds in a variety of research fields. Metallacrowns have been reported as single-molecule magnets (SMMs) and potential precursors for qubits, − magnetorefrigerants, , MOFs, cation and anion recognition agents, − and luminescent probes. − Establishing the solution stability of MCs, their selectivity for metal ions, and their guest recognition properties is essential for the design of functional compounds and materials based on MCs scaffolds. Therefore, more detailed characterization of the thermodynamic parameters associated with the assembly of MCs would be useful.…”

Section: Introductionmentioning

confidence: 99%

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

et al. 2019

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Four different crystal structures for quinolinehydroxamic acid (QuinHA) and picolinehydroxamic acid (PicHA) MCs with Cu(II) and Ni(II), and solution studies on the formation of Cu(II), Ni(II), and Zn(II) MC complexes with QuinHA, PicHA, and pyrazylohydroxamic acid (PyzHA) are described. In polynuclear complex 1, [Cu5(QuinHA-2H)4(NO3)(DMSO)4](NO3), the metallamacrocyclic cavity is formed by four Cu(II) ions and four doubly deprotonated hydroximate ligands, and the center of the cavity is occupied by the fifth Cu(II) ion coordinated by four hydroximate oxygen atoms. The complex 2, [Cu10(PicHA-2H)8(H2O)4(ClO4)3](ClO4)·4H2O, exhibits a dimeric structure based on two pentanuclear collapsed 12-MC-4 Cu4(PicHA-2H)4 fragments united by two chiral capping Cu(II) ions exo-coordinated to the peripheral vacant (O,O′) chelating units of each tetranuclear collapsed MC moiety. 3, [CaNi5(QuinHA-2H)5(H2O)2(Py)10](NO3)2, and 4, [CaNi5(PicHA-2H)5(DMF)2(Py)8](NO3)2, are planar 15-membered rings consisting of a PicHA or QuinHA ligand, respectively. To understand fully the correlation between species isolated in the solid state and those presented in solution, the solution equilibria were investigated, showing the dependence of the MCs topologies and stability constants (log β) on the ligand structure and metal ion.

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Section: Introductionmentioning

confidence: 99%

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

et al. 2019

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“…The magnetic behavior indicates the presence of magnetic anisotropy and/or population of the Ln(III) lowlying excited states. The contribution from Mn moments is negligibly small due to an antiferromagnetic coupling as concluded from magnetometric results of the reference compound YMn 4 [33].…”

Section: Methodsmentioning

confidence: 79%

“…The microcrystalline material stems from the same batch as the single crystals used for the x-ray absorption experiments. The magnetization of TbMn 4 shows a rapid increase with increasing field below 1 T followed by a slow, nearly linear increase without reaching saturation [33]. The magnetic behavior indicates the presence of magnetic anisotropy and/or population of the Ln(III) lowlying excited states.…”

Section: Methodsmentioning

confidence: 93%

“…LnMn 4 molecules with Ln=Tb(III) and Dy(III) have been synthesized as described in Ref. [33]. Magnetization properties result from magnetometry measurements [33] with a superconducting quantum interference device (SQUID) magnetometer on microcrystalline material.…”

Section: Methodsmentioning

confidence: 99%

“…[33]. Magnetization properties result from magnetometry measurements [33] with a superconducting quantum interference device (SQUID) magnetometer on microcrystalline material. The microcrystalline material stems from the same batch as the single crystals used for the x-ray absorption experiments.…”

Section: Methodsmentioning

confidence: 99%

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Anisotropy of 4f states in 3d−4f single-molecule magnets

et al. 2022

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Structural and Magnetic Properties of a {GdCu₅}₂Metallacrown Dimer with a Disulfonate Linker

Pavlishchuk,

Zeller,

Carrella

et al. 2024

Eur J Inorg Chem

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The complex {Na2(H2O)8[GdCu5(GlyHA)5(H2O)4L]2}L2·2.5DMF ·10.5H2O (1, where GlyHA2‐ = glycinehydroxamate, L2‐ = 4,4'‐bis(2‐sulfonatostyryl)biphenyl) was obtained as the outcome of the metathesis reaction of previously reported [GdCu5(GlyHA)5(CO3)(NO3)(H2O)5]·3.5H2O with an excess of the disulfonate's sodium salt. X‐Ray analysis of 1 shows a dimeric structure in which 15‐metallacrown‐5 units {GdCu5}3+ are arranged in an “edge‐to‐edge” manner by way of two linking disulfonates, L2‐. Magnetic studies of polycrystalline 1 over a temperature range of 2 – 300 K revealed both Gd‐‐Cu ferromagnetic and Cu‐‐Cu antiferromagnetic interactions within the metallacrown unit. Experimental χMTvs. T data for 1 were fitted using different theoretical models. A two‐J model, which takes into account both exchange interactions between adjacent copper(II) ions and the Gd‐Cu exchange interactions allows fitting of the χMTvs. T data in the whole temperature range. The values obtained for the exchange parameters are in accord with previously reported parameters for Ln(III)‐Cu(II) 15‐metallacrowns‐5. The 240 GHz powder EPR spectra for 1 were recorded at between 30 and 150 K.

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Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes

Cited by 9 publications

References 51 publications

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

Anisotropy of 4f states in 3d−4f single-molecule magnets

Structural and Magnetic Properties of a {GdCu₅}₂Metallacrown Dimer with a Disulfonate Linker

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Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes

Cited by 9 publications

References 51 publications

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

Explaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns

Anisotropy of 4f states in 3d−4f single-molecule magnets

Structural and Magnetic Properties of a {GdCu5}2Metallacrown Dimer with a Disulfonate Linker

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Structural and Magnetic Properties of a {GdCu₅}₂Metallacrown Dimer with a Disulfonate Linker