Observation of a large magnetocaloric effect in a 2D Gd(iii)-based coordination polymer

Biswas, Soumava; Adhikary, Amit; Goswami, Soumyabrata; Konar, Sanjit

doi:10.1039/c3dt51668g

Cited by 74 publications

(35 citation statements)

References 40 publications

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“…A series of Gd III complexes that contained 1D chains have been synthesized with Gd 2 O 3 and various carboxylate ligands under hydrothermal conditions. Magnetic investigations revealed that antiferromagnetic coupling occurred in compounds 1-3, whereas weak ferromagnetic coupling occurred in 4, which led to the presence 20] 358.36 AF (À0.12) 43.8 (7 T) 104.59 A C H T U N G T R E N N U N G [Gd 48 ] [21] 313.83 AF (À3.57) 43.6 (7 T) 120.7…”

Section: Discussionmentioning

confidence: 99%

Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Liu

Xie

Jia

et al. 2014

Chemistry An Asian Journal

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Four carboxylate-bridged Gd(III) complexes (1-4) with 1D/2D structures have been synthesized by using the hydrothermal reaction of Gd2O3 with various carboxylate ligands. Compounds 1 and 2 contained the same [2n] Gd(III)-OH ladders, but with different crystallographically independent Gd(III) ions, whilst the structures of compounds 3 and 4 were composed of [Gd4(μ3-OH)2(piv)8(H2O)2](2+) units and 1D ladder Gd(III) chains, respectively. Antiferromagnetic interactions occurred in compounds 1-3, owing to their small Gd-O-Gd angles, whereas ferromagnetic coupling occurred in compound 4, in which the Gd-O-Gd angles were larger. These complexes exhibited a distinct magnetocaloric effect (MCE), which was affected by their different magnetic densities and exchange interactions. Among these compounds, complex 4 presented the largest MCE (-ΔS(m)(max)=43.6 J kg(-1) K(-1)), the lowest M(w)/N(Gd) ratio (the highest magnetic density), and weak ferromagnetic coupling. Therefore, a lower M(w)/N(Gd) ratio and weaker exchange interactions (a smaller absolute value of θ) between Gd(III) ions resulted in a larger MCE for the Gd(III) complexes.

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Section: Discussionmentioning

confidence: 99%

Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Liu

Xie

Jia

et al. 2014

Chemistry An Asian Journal

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“…Hence Gd 3 + has the largest entropy per single ion as calculated from R lnA C H T U N G T R E N N U N G (2S+1) in which R is the gas constant. [7][8][9] However, Dy 3 + has a 6 H 15/2 ground-state term, S = 5/2, L = 5, so, the large orbital momentum generates high magnetic anisotropy and a large number of unpaired f electrons gives a high ground state. These are responsible for the high energy barrier for the reversal of magnetization in dysprosium and is thereby responsible for it exhibiting single-molecule magnet (SMM) behavior.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Two Discrete Ln₁₀ Nanoscopic Ladder‐Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation

Adhikary

Jena

Khatua

et al. 2014

Chemistry An Asian Journal

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Two unique lanthanide-based cages [Ln10(L)5(μ2-OH)6(H2O)22](Cl)4⋅7 H2O ([Gd10] and [Dy10]) have been synthesized by using a hydrazone-based ligand H4L (H4L=2,6-bis[(3-methoxysalicylidene)hydrazinecarbonyl]pyridine) and LnCl3⋅x H2O. Structural characterization of [Gd10] reveals an aesthetically pleasing self-assembly of five L(4-) and ten Gd(3+) ions forming a 2×[1×5] rectangular array. The ladder-shaped cage consists of three "rungs" and two "rails" that are occupied by five ligands. Six out of ten gadolinium centers act as rung locks. Further analysis revealed that three chloride ions are encapsulated inside each discrete [Gd10] molecule through hydrogen bonding and other noncovalent interactions. Both the complexes ([Gd10] and [Dy10]) were characterized by powder X-ray diffraction and thermogravimetric analysis, which shows that they are isostructural in nature. Magnetic investigations reveal that [Gd10] is a good candidate for magnetic refrigeration with a significant entropy change (-ΔS(m)) of 37.4 J kg(-1) K(-1) for an applied field of 7 T and at 3 K. Whereas [Dy10] shows single-molecule-magnet-like behavior.

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“…[12][13][14] It was found that the cryogenic magnetocaloric effect in molecular nanomagnets, which originates from the Schottky anomaly, can be considerably larger than that of the classic metallic refrigerants. [15] The grounds for the good cooling performance of the reported clusters or frameworks are large spins, negligible magnetic anisotropy, dominant ferromagnetic exchange and large magnetic density. [6] In systems with long-range order of magnetic moments, |ΔS| achieves a maximum at the magnetic ordering temperature T c .…”

Section: Introductionmentioning

confidence: 99%

“…Studies on MCE in molecular materials mainly concerned high‐spin molecular clusters and metal–organic frameworks (MOFs) . It was found that the cryogenic magnetocaloric effect in molecular nanomagnets, which originates from the Schottky anomaly, can be considerably larger than that of the classic metallic refrigerants . The grounds for the good cooling performance of the reported clusters or frameworks are large spins, negligible magnetic anisotropy, dominant ferromagnetic exchange and large magnetic density .…”

Section: Introductionmentioning

confidence: 99%

The Magnetocaloric Effect in the Thin Film of a Prussian Blue Analogue

et al. 2017

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Investigation of the magnetocaloric effect (MCE) in the thin film of nickel hexacyanochromate obtained by “layer‐by‐layer” deposition is reported. This compound shows a sharp phase transition to a long‐range ferromagnetically ordered state at Tc = 66 K. In order to check the shape anisotropy effect, the properties of the thin film were investigated for the sample aligned parallel and perpendicular to the direction of an applied magnetic field. The demagnetizing field was smaller than the fields used to observe the MCE. For the fields higher than 1 T, values of the magnetic entropy change obtained for both film orientations are similar reaching 7.43 J kg–1 K–1 and 7.07 J kg–1 K–1 at µ0H = 5 T for parallel and perpendicular orientations, respectively. The n exponent characterizing the field dependence of the entropy change is the same and equals 0.72 ± 0.02 at Tc. Scaling analysis to obtain the master curves of the entropy temperature dependence was performed for both film orientations.

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Observation of a large magnetocaloric effect in a 2D Gd(iii)-based coordination polymer

Abstract: A new 2D Gd(III)-based coordination polymer has close to the highest cryogenic magnetocaloric effect of any MOF reported so far. The experimental results reveal its structural features and magnetic properties.

Cited by 74 publications

References 40 publications

Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Synthesis and Characterization of Two Discrete Ln₁₀ Nanoscopic Ladder‐Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation

The Magnetocaloric Effect in the Thin Film of a Prussian Blue Analogue

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Observation of a large magnetocaloric effect in a 2D Gd(iii)-based coordination polymer

Abstract: A new 2D Gd(III)-based coordination polymer has close to the highest cryogenic magnetocaloric effect of any MOF reported so far. The experimental results reveal its structural features and magnetic properties.

Cited by 74 publications

References 40 publications

Low‐Dimensional Carboxylate‐Bridged GdIII Complexes for Magnetic Refrigeration

Low‐Dimensional Carboxylate‐Bridged GdIII Complexes for Magnetic Refrigeration

Synthesis and Characterization of Two Discrete Ln10 Nanoscopic Ladder‐Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation

The Magnetocaloric Effect in the Thin Film of a Prussian Blue Analogue

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Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Low‐Dimensional Carboxylate‐Bridged Gd^III Complexes for Magnetic Refrigeration

Synthesis and Characterization of Two Discrete Ln₁₀ Nanoscopic Ladder‐Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation