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Special Issue "New Findings of Magnetic Metal-Organic Framework Compounds"

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (20 November 2021) | Viewed by 5060

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Dr. Marijana Jurić

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Division of Materials Chemistry, Ruđer Bošković Institute, 10000 Zagreb, Croatia
Interests: metal–organic compounds; structural and thermal analysis; magnetic and electrical properties; mixed metal oxides
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Dear Colleagues,

Metal-organic frameworks (MOFs) or coordination polymers (CPs) have been extensively studied due to a large variety of topologies and structures leading to a diverse platform of physical and chemical properties, which make them prototypes of multifunctional molecular materials.

Magnetic properties can be brought into MOFs by choosing suitable metal centres, organic linkers, and the manner of their connection, or by introducing functional molecules in the pores. In general, a primary aim of the investigation of magnetic materials is the upgrading of the properties of magnets and the exploration of new functions, especially together with other beneficial occurrence.

This following Special Issue of Materials will cover recent progress, novelties, and important findings regarding the magnetic properties of the metal-organic framework compounds. Publishing contributions of original research articles, focused on the synthesis and full characterizations based on the magnetic properties, both experimental and theoretical, of the above systems is our primary goal. Researches on multifunctional magnetic MOFs studied through an interdisciplinary approach are especially welcome.

Dr. Marijana Jurić
Guest Editor

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Keywords

Metal-organic frameworks
Structural diversity and topology
Molecule-based magnets
Multifunctional molecular magnets
Photomagnetism and optical activity
Spontaneous magnetization
Phase transitions

Published Papers (3 papers)

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Research

Open AccessArticle

Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility

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Materials 2021, 14(19), 5543; https://doi.org/10.3390/ma14195543 - 24 Sep 2021

Viewed by 1169

Abstract

A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {[NH(CH₃)(C₂H₅)₂][FeCl₂(C₂O₄)]}_n (1), exhibits remarkable humidity-sensing properties and very high proton conductivity at room temperature (2.70 × 10⁻⁴ (Ω·cm)⁻¹ at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups (J = −7.58(9) cm⁻¹). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains [FeCl₂(C₂O₄)]_nⁿ⁻ and interposed diethylmethylammonium cations (C₂H₅)₂(CH₃)NH⁺, which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients. Full article

(This article belongs to the Special Issue New Findings of Magnetic Metal-Organic Framework Compounds)

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Open AccessArticle

Magnetoelectric Multiferroicity and Magnetic Anisotropy in Guanidinium Copper(II) Formate Crystal

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Materials 2021, 14(7), 1730; https://doi.org/10.3390/ma14071730 - 01 Apr 2021

Cited by 2 | Viewed by 1768

Abstract

Hybrid metal-organic compounds as relatively new and prosperous magnetoelectric multiferroics provide opportunities to improve the polarization, magnetization and magneto-electric coupling at the same time, which usually have some limitations in the common type-I and type-II multiferroics. In this work we investigate the crystal [...] Read more.

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and give novel insights concerning the structure, magnetic, electric and magneto-electric behaviour of this interesting material. Detailed analysis of crystal structure at 100 K is given. Magnetization points to the copper (II) formate spin-chain phase that becomes ordered below 4.6 K into the canted antiferromagnetic (AFM) state, as a result of super-exchange interaction over different formate bridges. The performed ab-initio colinear density functional theory (DFT) calculations confirm the AFM-like ground state as a first approximation and explain the coupling of spin-chains into the AFM ordered lattice. In versatile measurements of magnetization of a crystal, including transverse component besides the longitudinal one, very large anisotropy is found that might originate from canting of the coordination octahedra around copper (II) in cooperation with the canted AFM order. With cooling down in zero fields the generation of spontaneous polarization is observed step-wise below 270 K and 210 K and the effect of magnetic field on its value is observed also in the paramagnetic phase. Measured polarization is somewhat smaller than the DFT value in the c-direction, possibly due to twin domains present in the crystal. The considerable magneto-electric coupling below the magnetic transition temperature is measured with different orientations of the crystal in magnetic field, giving altogether the new light onto the magneto-electric effect in this material. Full article

(This article belongs to the Special Issue New Findings of Magnetic Metal-Organic Framework Compounds)

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Open AccessArticle

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C₂O₄)₃]³⁻ Building Block

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Materials 2020, 13(23), 5341; https://doi.org/10.3390/ma13235341 - 25 Nov 2020

Cited by 6 | Viewed by 1626

Abstract

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C₂O₄)]·1.5H₂O}_n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu₃(bpy)₃(CH₃OH)(H₂O)(C₂O₄)₄][Cu(bpy)Cr(C₂O₄)₃]·CH₂Cl₂·CH₃OH·H₂O}_n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C₂O₄)]_n of 1, with intra-chain super-exchange interaction ? = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C₂O₄)₃]_nⁿ⁻ (Cr2–Cu4) with alternating [Cr(C₂O₄)₃]³⁻ and [Cu(bpy)]²⁺ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H₂O)(µ-C₂O₄)Cu(bpy)(CH₃OH)]²⁺ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) comprising three different metal centers (Ca²⁺, Cr³⁺ and Cu²⁺) oxalate-bridged, contains Ca²⁺ atoms as nodes connected with four Cr³⁺ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (6⁶) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu^IICr^III], whose mutual interaction could possibly originate through the spin polarization of Ca²⁺ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2. Full article

(This article belongs to the Special Issue New Findings of Magnetic Metal-Organic Framework Compounds)

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