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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

1
Ruđer Bošković Institute, Bijenička cesta 54, 10000 Zagreb, Croatia
2
Department of Physics, Faculty of Science, University of Zagreb, Bijenička cesta 32, 10000 Zagreb, Croatia
*
Author to whom correspondence should be addressed.
Materials 2020, 13(23), 5341; https://doi.org/10.3390/ma13235341
Received: 19 October 2020 / Revised: 17 November 2020 / Accepted: 19 November 2020 / Published: 25 November 2020
(This article belongs to the Special Issue New Findings of Magnetic Metal-Organic Framework Compounds)
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 Cu1Cu2 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. View Full-Text
Keywords: coordination polymers; oxalate-bridged; crystal structure; electrical property; magnetic property coordination polymers; oxalate-bridged; crystal structure; electrical property; magnetic property
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MDPI and ACS Style

Kanižaj, L.; Šenjug, P.; Pajić, D.; Pavić, L.; Molčanov, K.; Jurić, M. 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. Materials 2020, 13, 5341. https://doi.org/10.3390/ma13235341

AMA Style

Kanižaj L, Šenjug P, Pajić D, Pavić L, Molčanov K, Jurić M. 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. Materials. 2020; 13(23):5341. https://doi.org/10.3390/ma13235341

Chicago/Turabian Style

Kanižaj, Lidija, Pavla Šenjug, Damir Pajić, Luka Pavić, Krešimir Molčanov, and Marijana Jurić. 2020. "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" Materials 13, no. 23: 5341. https://doi.org/10.3390/ma13235341

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