Multifunctional properties of {CuII2LnIII2} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity

Li, Hongdao; Jing, Pei; Lu, Jiao; Liu, Xi; Wang, Qi; Ding, Lifeng; Wang, Wenmin; Song, Zhenjun

doi:10.1039/d0dt04344c

Cited by 28 publications

(11 citation statements)

References 55 publications

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“…Moreover, instead of using randomly chosen pairs, a specific combination of 3d and 4f metals with the aim of culminating their characteristic properties starts to dominate the design strategy, aiming to kill two birds with one stone . One such popular combination for a set of 3d–4f complexes would be magnetism and luminescence, which also coincides with the broad theme of this work. − …”

Section: Introductionmentioning

confidence: 52%

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: 52%

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

et al. 2022

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“…[ 36–40 ] Interestingly, complexes 1 and 2 show entirely different natures in comparison with those reported Cu‐Ln clusters. [ 41–43 ] Two Dy III and two Cu II are linked by six O atoms to construct a Z‐shaped Cu‐(O) 2 ‐Dy‐(O) 2 ‐Dy‐(O) 2 ‐Cu skeleton.…”

Section: Resultsmentioning

confidence: 99%

Two tetranuclear Cu₂Ln₂ (Ln = Dy, Tb) heterometallic complexes: Structure, solution behavior, and magnetic properties

Zhang

Zhu

et al. 2021

Applied Organom Chemis

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Two tetranuclear 3d–4f heterometallic complexes [Cu2Ln2(NO3)4(OAc)2L4] (Ln = Dy 1, Tb 2) were obtained under solvothermal reactions of 1‐amino‐propan‐2‐ol (HL) with [Cu2(OAc)4(H2O)2] and Ln (NO3)3·5H2O. The structural analyses confirmed a centrosymmetric Z‐shaped skeleton for them with the peripheral positions occupied by two Cu (II) ions. The neighboring two lanthanide ions, as well as the neighboring ions of Ln (III) and Cu (II), are all double‐bridged through two O atoms. The detailed dynamic magnetic investigation showed slow magnetic relaxation behaviors for both complexes with an energy barrier of 1.35(2) and 2.02(4) K for 1 and 2, respectively. Furthermore, it revealed from the electrospray mass spectrometry (ESI‐MS) that complexes 1 and 2 easily undergo dimerization in solution.

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“…42 Pioneering SCM systems such as [Co(hfac) 2 (NITPhOMe)] 42 b and [Dy(hfac) 3 (NIT-C 6 H 4 OPh)] ∞ 42 e , f reported by R. Sessoli and D. Gatteschi et al have been set as archetypes for magnetism investigation and pave the way for the study of follow-up nitroxide radical–Ln SMMs. 43–56 Different from the nitrogen-based Rad–Ln SMMs which often contain the [Dy(Cp) 2 ] + fragment, chemists favor the neutral [Dy(hfac) 3 ] motif to design nitronyl nitroxide-based 4f SMMs. The text-book example of 2p–4f-SMM [Dy(hfac) 3 (NITpPy)] 2 ( 22 ) was first reported by G. Poneti et al in 2007.…”

Section: The Development Of Ln–rad Systemsmentioning

confidence: 99%

Lanthanide–radical single-molecule magnets: current status and future challenges

Tong

2023

Chem. Commun.

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Multifunctional properties of {CuII2LnIII2} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity

Abstract: A family of 3d–4f heterometallic ring-shaped clusters on the basis of a nitrogen-rich nitronyl nitroxide radical have been obtained, and they feature polyfunctionality including magnetic properties, thermodynamics and luminescence behavior.

Cited by 28 publications

References 55 publications

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Two tetranuclear Cu₂Ln₂ (Ln = Dy, Tb) heterometallic complexes: Structure, solution behavior, and magnetic properties

Lanthanide–radical single-molecule magnets: current status and future challenges

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Multifunctional properties of {CuII2LnIII2} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity

Abstract: A family of 3d–4f heterometallic ring-shaped clusters on the basis of a nitrogen-rich nitronyl nitroxide radical have been obtained, and they feature polyfunctionality including magnetic properties, thermodynamics and luminescence behavior.

Cited by 28 publications

References 55 publications

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln2Zn6 Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln2Zn6 Clusters

Two tetranuclear Cu2Ln2 (Ln = Dy, Tb) heterometallic complexes: Structure, solution behavior, and magnetic properties

Lanthanide–radical single-molecule magnets: current status and future challenges

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Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Synergistic Experimental and Theoretical Studies of Luminescent–Magnetic Ln₂Zn₆ Clusters

Two tetranuclear Cu₂Ln₂ (Ln = Dy, Tb) heterometallic complexes: Structure, solution behavior, and magnetic properties