Cyano-Bridged 4f-3d Coordination Polymers with a Unique Two-Dimensional Topological Architecture and Unusual Magnetic Behavior

Ma, Bao‐Qing; Gao, Song; Su, Gang; Xu, Guangyang

doi:10.1002/1521-3757(20010119)113:2<448::aid-ange448>3.0.co;2-3

Cited by 27 publications

(5 citation statements)

References 44 publications

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“…There are antiferromagnetically coupled triangular sublattices within the layered Gd 3+ wheel‐cluster network. Such a frustrated spin geometry has ever been inferred to play a crucial role in the field‐induced frequency‐dependent magnetic behaviors of some lanthanide complexes 27. However, with the development in magnetochemistry of lanthanide complexes, this field‐induced relaxation process tends to be explained by the magnetic behavior of an isolated ion, the lifting of the Kramer degeneracy by the applied magnetic field is responsible for this magnetic phenomenon 28.…”

Section: Resultsmentioning

confidence: 99%

Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands

Cheng

Zhang

Zheng

et al. 2007

Chemistry A European J

125

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A new series of heterolanthanide(III)-copper(I) wheel-cluster complexes [Ln6(micro3-O)2](IN)18-[Cu8(micro4-I)2(micro2-I)3].H3O (IN=isonicotinate; Ln=Y 1, Nd 2, Dy 3, Gd 4, Sm 5, Eu 6, Tb 7) were prepared by hydrothermal reaction at low pH. X-ray crystallographic studies reveal that two unusual trinuclear [Ln3(micro3-O)] and tetranuclear [Cu4(micro4-I)] cores are successfully used as secondary building units to make two different nanosized wheels [Ln18(micro3-O)6(CO2)48](6-), {Ln18}, and [Cu24(micro4-I)6(micro2-I)12]6+, {Cu24}, with 12-rings and a diameter of 26.7 and 26.4 A, respectively. The wheels are further assembled into two-dimensional (2D) {Ln18} and {Cu24} networks, the linkages between two distinct layered networks of {Ln18} and {Cu24} wheels by IN pillars along the c axis giving a series of unprecedented three-dimensional (3D) sandwich frameworks. To our knowledge, compounds 1-7 are the first examples containing two different layered networks of nanosized Ln and transition metal (TM) wheels in wheel-cluster chemistry. The IR, UV/Vis, thermogravimetric analysis (TGA), luminescent, and magnetic properties of these complexes were also studied.

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Section: Resultsmentioning

confidence: 99%

Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands

Cheng

Zhang

Zheng

et al. 2007

Chemistry A European J

125

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“…In the very beginning of our research, a DC field dependent slow magnetic relaxation was observed in the Nd III containing 2D coordination polymer. 27 The slow magnetic relaxation was at first attributed to the presence of frustration which is unveiled by the static DC field. 28 This DC field induced slow magnetic relaxation was later found to be rather general in lanthanide containing complexes with or without 3d spin carriers.…”

Section: Survey Of 4f-simsmentioning

confidence: 99%

Understanding the Magnetic Anisotropy toward Single-Ion Magnets

et al. 2016

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Single-molecule magnets (SMMs) can retain their magnetization status preferentially after removal of the magnetic field below a certain temperature. The unique property, magnetic bistable status, enables the molecule-scale SMM to become the next-generation high-density information storage medium. SMMs' new applications are also involved in high-speed quantum computation and molecular spintronics. The development of coordination chemistry, especially in transition metal (3d) and lanthanide (4f) complexes, diversifies SMMs by introducing new ones. In both 3d and 4f SMMs, the ligands play a fundamental role in determining the SMMs' magnetic properties. The strategies for rationally designing and synthesizing high-performance SMMs require a comprehensive understanding of the effects of a crystal field. In this Account, we focus mainly on the magneto-structural correlations of 4f or 3d single-ion magnets (SIMs), within which there is only one spin carrier. These one-spin carrier complexes benefit from getting rid of exchange interactions and relatively large distances of magnetic centers in the lattice, providing the ease to construct high-performance SIMs from the crystal field perspective. We will briefly introduce the crystal field approach for 4f or 3d complexes and then the magnetic anisotropy analysis via the displaced-charge electrostatic model. This idea has been proposed for years, and the related work is also highlighted. The angular-resolved magnetometry method, predominating in determining the magnetic anisotropic axes direction, is discussed. We also give a brief introduction of the quantum chemistry ab initio method, which has shown to be powerful in understanding the magnetic anisotropy and low-lying states. In the constructing and characterizing part, we give an overview of the SIMs based on lanthanide and transition ions, reported by our group in the past 5 years. In the 4f-SIMs survey, we discuss how β-diketonates and cyclomultienes, and their combination, as ligands to influence magnetic anisotropy and provide some suggestion on designing SIMs based on different lanthanide ions. In the 3d-SIMs survey, we fully discuss the correlation between zero-field-splitting parameter D and molecular geometrical angle parameters. Finally, we lay out the challenges and further development of SIMs. We hope the understanding we provide about single-ion magnetic properties will be helpful to design high-performance SMMs.

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“…42,43 Also, trivalent Ln III -MOFs can be considered to be promising molecular magnetic materials because they have large magnetic anisotropy and strong spin−orbit coupling except for gadolinium(III)-based MOFs. 44,45 Among the organic linkers used for the construction of Ln-MOFs, rigid polycarboxylates such as furandicarboxylic, 46−49 thiophenedicarboxylic, 50−52 pyridinedicarboxylic, 53−57 isophthalic, 58,59 terephthalic, 60−63 2,6-naphthalenedicarboxylic, 64−67 and trimesic 68−71 acids are of special interest. They have been widely exploited for the synthesis of Ln-MOFs.…”

Section: ■ Introductionmentioning

confidence: 99%

A Series of Lanthanide-Based Metal–Organic Frameworks Derived from Furan-2,5-dicarboxylate and Glutarate: Structure-Corroborated Density Functional Theory Study, Magnetocaloric Effect, Slow Relaxation of Magnetization, and Luminescent Properties

Kumar

Kariem

et al. 2019

Inorg. Chem.

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Herein, through a dual-ligand strategy, we report eight isorecticular lanthanide(III) furan-2,5-dicarboxylic acid metal−organic frameworks (Ln-MOFs) with the general formula {[Ln(2, Gd (3), Tb (4), Dy (5), Ho (6), Er (7), and Yb (8); 2,5-FDA 2− = furan-2,5-dicarboxylate and Glu 2− = glutarate; x = 0.5 for 1, 2, and 4 and x = 0 for 3 and 5−8], synthesized under solvothermal conditions by using an N,N′-dimethylformamide/H 2 O mixed solvent system. Crystallographic data reveal that all eight Ln-MOFs 1−8 crystallize in the orthorhombic Pnma space group. All of the MOFs are isostructural as well as isomorphous with distorted monocapped squareantiprismatic geometry around the Ln1 metal center. In Ln-MOFs 1−8, the 2,5-FDA 2− and Glu 2− ligands exhibit μ 2 -κ 4 ,η 1 :η 1 :η 1 :η 1 and μ 3 -κ 5 ,η 2 :η 1 :η 1 :η 1 coordination modes, respectively. Topologically, assembled Ln-MOFs 1−8 consist of the 2D cem topological type. The designed Ln-MOFs 1−8 are further explored for structure-corroborated density functional theory study. Meanwhile, room temperature photoluminescence properties of Ln-MOFs 2 and 4 and magnetic properties of Ln-MOFs 3 and 5 have been explored in detail. A highly intense, ligand-sensitized, Ln 3+ f−f photoluminescence emission is exhibited by Ln-MOFs 2 [Eu 3+ (red emission)] and 4 [Tb 3+ (green emission)]. Magnetic studies suggest weak antiferro-and ferromagnetic interactions between adjacent Gd III ions in Ln-MOF 3, thereby displaying a large magnetocaloric effect. The magnetic data measured at T = 2 K and ΔH = 30 kOe depict that the −ΔS m value per unit mass reaches 32.1 J kg −1 K −1 , which is larger than most of the Gd III -based complexes reported. The alternating-current susceptibility measurements on Ln-MOF 5 revealed that out-of-phase signals are frequency-and temperature-dependent under both 0 and 2 kOe direct-current fields, thereby suggesting a typical slow magnetic relaxation behavior with two relaxation processes. This is further supported by the Cole−Cole plots at 2.4−6 K.

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Cyano-Bridged 4f-3d Coordination Polymers with a Unique Two-Dimensional Topological Architecture and Unusual Magnetic Behavior

Cited by 27 publications

References 44 publications

Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands

Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands

Understanding the Magnetic Anisotropy toward Single-Ion Magnets

A Series of Lanthanide-Based Metal–Organic Frameworks Derived from Furan-2,5-dicarboxylate and Glutarate: Structure-Corroborated Density Functional Theory Study, Magnetocaloric Effect, Slow Relaxation of Magnetization, and Luminescent Properties

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Cyano-Bridged 4f-3d Coordination Polymers with a Unique Two-Dimensional Topological Architecture and Unusual Magnetic Behavior

Cited by 27 publications

References 44 publications

Linking Two Distinct Layered Networks of Nanosized {Ln18} and {Cu24} Wheels through Isonicotinate Ligands

Linking Two Distinct Layered Networks of Nanosized {Ln18} and {Cu24} Wheels through Isonicotinate Ligands

Understanding the Magnetic Anisotropy toward Single-Ion Magnets

A Series of Lanthanide-Based Metal–Organic Frameworks Derived from Furan-2,5-dicarboxylate and Glutarate: Structure-Corroborated Density Functional Theory Study, Magnetocaloric Effect, Slow Relaxation of Magnetization, and Luminescent Properties

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Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands

Linking Two Distinct Layered Networks of Nanosized {Ln₁₈} and {Cu₂₄} Wheels through Isonicotinate Ligands