A new family of Fe4Ln4 (Ln = DyIII, GdIII, YIII) wheel type complexes with ferromagnetic interaction, magnetocaloric effect and zero-field SMM behavior

Mondal, Arpan; Raizada, Mukul; Sahu, Pradip Kumar; Konar, Sanjit

doi:10.1039/d1qi00781e

Cited by 13 publications

(10 citation statements)

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“…Single-molecule magnet (SMM) and magnetocaloric effect (MCE), inter alia , are the two most important lanthanide-magnetism topics that have tantalized the attention of both chemists and physicists in recent years. − The Dy 3+ compounds, because of their significant anisotropy arising from large unquenched orbital angular momentum and a high energy reversal barrier, more-often-than-not show slow magnetic relaxation and dominate SMM studies. − On the other hand, the Gd 3+ ion, by virtue of its large spin-only magnetic moment, weak superexchange interaction, and quenched orbital momentum, predominates the recent quest for low-cost, environmentally benign cryogenic technology using MCE-based magnetic refrigeration. − Notwithstanding their individual magnetic features, the combination of Dy 3+ and Gd 3+ with transition metals is often found to excel the magnetic behavior. − …”

Section: Introductionmentioning

confidence: 99%

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

et al. 2022

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The present work is part of our ongoing quest for developing functional inorganic complexes using unorthodox pyridyl–pyrazolyl-based ligands. Accordingly, we report herein the synthesis, characterization, and luminescence and magnetic properties of four 3d–4f mixed-metal complexes with a general core of Ln2Zn6 (Ln = Dy, Gd, Tb, and Eu). In stark contrast to the popular wisdom of using a compartmental ligand with separate islands of hard and soft coordinating sites for selective coordination, we have vindicated our approach of using a ligand with overcrowded N-coordinating sites that show equal efficiency with both 4f and 3d metals toward multinuclear cage-cluster formation. The encouraging red and green photolumiscent features of noncytotoxic Eu2Zn6 and Tb2Zn6 complexes along with their existence in nanoscale dimension have been exploited with live-cell confocal microscopy imaging of human breast adenocarcinoma (MCF7) cells. The magnetic features of the Dy 2 Zn 6 complex confirm the single-molecule-magnet behavior with befitting frequency- and temperature-dependent out-of-phase signals along with an U eff value of ∼5 K and a relaxation time of 8.52 × 10–6 s. The Gd 2 Zn 6 complex, on the other hand, shows cryogenic magnetic refrigeration with an entropy change of 11.25 J kg–1 K–1 at a magnetic field of 7 T and at 2 K. Another important aspect of this work reflects the excellent agreement between the experimental results and theoretical calculations. The theoretical studies carried out using the broken-symmetry density functional theory, ORCA suite of programs, and MOLCAS calculations using the complete-active-space self-consistent-field method show an excellent synergism with the experimentally measured magnetic and spectroscopic data.

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Section: Introductionmentioning

confidence: 99%

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

et al. 2022

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“…As we know, 4f metal ions are more attracted to hard atoms such as O and F, while 3d ions are likely to bind soft atoms such as N and S according to the hard–soft acid–base principle . Thus, previously established methodologies for mixed 3d-4f metal rings are of great importance to synthesize Sc–Gd heterometallic rings. − We found that it is necessary to reduce the amount of base for the synthesis of smaller rings compared with the larger ones. In fact, the H 2 mdea ligands are fully deprotonated in Sc 8 Gd 8 and Sc 6 Gd 6, while in Sc 4 Gd 4 , there are two H 2 mdea ligands that are not fully deprotonated, in which only one proton is removed.…”

Section: Resultsmentioning

confidence: 99%

{Sc_nGd_n} Heterometallic Rings: Tunable Ring Topology for Spin-Wave Excitations

et al. 2022

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Data carriers using spin waves in spintronic and magnonic logic devices offer operation at low power consumption and free of Joule heating yet requiring noncollinear spin structures of small sizes. Heterometallic rings can provide such an opportunity due to the controlled spin-wave transmission within such a confined space. Here, we present a series of {Sc n Gd n } (n = 4, 6, 8) heterometallic rings, which are the first Sc–Ln clusters to date, with tunable magnetic interactions for spin-wave excitations. By means of time- and temperature-dependent spin dynamics simulations, we are able to predict distinct spin-wave excitations at finite temperatures for Sc 4 Gd 4 , Sc 6 Gd 6 , and Sc 8 Gd 8 . Such a new model is previously unexploited, especially due to the interplay of antiferromagnetic exchange, dipole–dipole interaction, and ring topology at low temperatures, rendering the importance of the latter to spin-wave excitations.

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“…However, by comparing the magnetic data and the behavior of 1 and 2, it is found that the initial decrease of the χ m T products on cooling of 2 is due to the depopulation of the Stark levels of the Dy III ion. 50 In addition, the increase of the χ m T products below 44 K is due to the ferromagnetic coupling between the Co II ions in 2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Two-Dimensional Metal Azides Constructed by a Ln@Co₆Cluster and Disordered Co₃(N₃)₁₁Units

Sun

Zhao

Liu

2022

Crystal Growth & Design

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Two-dimensional metal azides [LnCo 9 (Pzc) 6 (OH) 3 (N 3 ) 11 •2(CH 3 OH)•2H 2 O] n (Ln = Gd for 1 and Dy for 2) have been solvothermally prepared. In 1 and 2, a heptanuclear Ln@Co 6 cluster is formed in which a nonacoordinate D 3h Ln III ion is encapsulated in a Co 6 cage. The heptanuclear Ln@Co 6 clusters are linked by disordered Co 3 (N 3 ) 11 units through the connection of the azide to give a 2D metal azide layer. Magnetic studies indicate ferromagnetic magnetic interactions between the ions in 1 and 2.

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A new family of Fe₄Ln₄ (Ln = Dy^III, Gd^III, Y^III) wheel type complexes with ferromagnetic interaction, magnetocaloric effect and zero-field SMM behavior

Cited by 13 publications

References 100 publications

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

{Sc_nGd_n} Heterometallic Rings: Tunable Ring Topology for Spin-Wave Excitations

Two-Dimensional Metal Azides Constructed by a Ln@Co₆Cluster and Disordered Co₃(N₃)₁₁Units

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A new family of Fe4Ln4 (Ln = DyIII, GdIII, YIII) wheel type complexes with ferromagnetic interaction, magnetocaloric effect and zero-field SMM behavior

Cited by 13 publications

References 100 publications

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln2Zn6 Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln2Zn6 Clusters

{ScnGdn} Heterometallic Rings: Tunable Ring Topology for Spin-Wave Excitations

Two-Dimensional Metal Azides Constructed by a Ln@Co6Cluster and Disordered Co3(N3)11Units

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A new family of Fe₄Ln₄ (Ln = Dy^III, Gd^III, Y^III) wheel type complexes with ferromagnetic interaction, magnetocaloric effect and zero-field SMM behavior

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

{Sc_nGd_n} Heterometallic Rings: Tunable Ring Topology for Spin-Wave Excitations

Two-Dimensional Metal Azides Constructed by a Ln@Co₆Cluster and Disordered Co₃(N₃)₁₁Units