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New Findings of Magnetic Metal-Organic Framework Compounds
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New Findings of Magnetic Metal-Organic Framework Compounds

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 9144

Special Issue Editor

Dr. Marijana Jurić

E-Mail Website
Guest Editor
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

Special Issue Information

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

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Published Papers (3 papers)

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Research

12 pages, 2811 KiB  
Article
Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility
by Sanja Burazer, Krešimir Molčanov, Ana Šantić, Teodoro Klaser, Emmanuel Wenger, Damir Pajić, Zvonko Jagličić, Jasminka Popović and Marijana Jurić
Materials 2021, 14(19), 5543; https://doi.org/10.3390/ma14195543 - 24 Sep 2021
Cited by 4 | Viewed by 2208
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 [...] Read more.
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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19 pages, 2162 KiB  
Article
Magnetoelectric Multiferroicity and Magnetic Anisotropy in Guanidinium Copper(II) Formate Crystal
by Pavla Šenjug, Jure Dragović, Filip Torić, Ivor Lončarić, Vito Despoja, Kristina Smokrović, Edi Topić, Ivica Đilović, Mirta Rubčić and Damir Pajić
Materials 2021, 14(7), 1730; https://doi.org/10.3390/ma14071730 - 1 Apr 2021
Cited by 7 | Viewed by 3143
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.
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 of guanidinium copper (II) formate [C(NH2)3]Cu(HCOO)3 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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20 pages, 5173 KiB  
Article
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
by Lidija Kanižaj, Pavla Šenjug, Damir Pajić, Luka Pavić, Krešimir Molčanov and Marijana Jurić
Materials 2020, 13(23), 5341; https://doi.org/10.3390/ma13235341 - 25 Nov 2020
Cited by 12 | Viewed by 2885
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]·CH2Cl [...] Read more.
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 J = (−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 [CuIICrIII], 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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