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Article

Slow Magnetic Relaxation in {[CoCxAPy)] 2.15 H2O}n MOF Built from Ladder-Structured 2D Layers with Dimeric SMM Rungs

1
Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain
2
Department of Mechanical Engineering, Escola Universitària Salesiana de Sarrià (EUSS), Passeig de Sant Joan Bosco, 74, 08017 Barcelona, Spain
3
Centro Universitario de la Defensa, Ctra. de Huesca s/n, 50090 Zaragoza, Spain
4
Department of Inorganic Polymers, “Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, 700487 Iasi, Romania
5
Institute of Chemistry, Academy of Sciences of Moldova, Academiei 3, MD-2028 Chisinau, Moldova
*
Author to whom correspondence should be addressed.
Constantin Turta passed away on 23 March 2015.
Academic Editors: Raed Abu-Reziq and Dawid Pinkowicz
Molecules 2021, 26(18), 5626; https://doi.org/10.3390/molecules26185626
Received: 21 June 2021 / Revised: 3 September 2021 / Accepted: 10 September 2021 / Published: 16 September 2021
(This article belongs to the Special Issue 2D Magnetic Molecular Materials)
We present the magnetic properties of the metal-organic framework {[CoCxAPy]·2.15 H2O}n (Cx = bis(carboxypropyl)tetramethyldisiloxane; APy = 4,4`-azopyridine) (1) that builds up from the stacking of 2D coordination polymers. The 2D-coordination polymer in the bc plane is formed by the adjacent bonding of [CoCxAPy] 1D two-leg ladders with Co dimer rungs, running parallel to the c-axis. The crystal packing of 2D layers shows the presence of infinite channels running along the c crystallographic axis, which accommodate the disordered solvate molecules. The Co(II) is six-coordinated in a distorted octahedral geometry, where the equatorial plane is occupied by four carboxylate oxygen atoms. Two nitrogen atoms from APy ligands are coordinated in apical positions. The single-ion magnetic anisotropy has been determined by low temperature EPR and magnetization measurements on an isostructural compound {[Zn0.8Co0.2CxAPy]·1.5 CH3OH}n (2). The results show that the Co(II) ion has orthorhombic anisotropy with the hard-axis direction in the C2V main axis, lying the easy axis in the distorted octahedron equatorial plane, as predicted by the ab initio calculations of the g-tensor. Magnetic and heat capacity properties at very low temperatures are rationalized within a S* = 1/2 magnetic dimer model with anisotropic antiferromagnetic interaction. The magnetic dimer exhibits slow relaxation of the magnetization (SMM) below 6 K in applied field, with a tlf ≈ 2 s direct process at low frequencies, and an Orbach process at higher frequencies with U/kB = 6.7 ± 0.5 K. This compound represents a singular SMM MOF built-up of Co-dimers with an anisotropic exchange interaction. View Full-Text
Keywords: MOF; single molecule magnet; slow magnetic relaxation; 2D coordination polymer; anisotropic exchange; magnetic dimer; Co(II) dimer MOF; single molecule magnet; slow magnetic relaxation; 2D coordination polymer; anisotropic exchange; magnetic dimer; Co(II) dimer
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MDPI and ACS Style

Arauzo, A.; Bartolomé, E.; Luzón, J.; Alonso, P.J.; Vlad, A.; Cazacu, M.; Zaltariov, M.F.; Shova, S.; Bartolomé, J.; Turta, C. Slow Magnetic Relaxation in {[CoCxAPy)] 2.15 H2O}n MOF Built from Ladder-Structured 2D Layers with Dimeric SMM Rungs. Molecules 2021, 26, 5626. https://doi.org/10.3390/molecules26185626

AMA Style

Arauzo A, Bartolomé E, Luzón J, Alonso PJ, Vlad A, Cazacu M, Zaltariov MF, Shova S, Bartolomé J, Turta C. Slow Magnetic Relaxation in {[CoCxAPy)] 2.15 H2O}n MOF Built from Ladder-Structured 2D Layers with Dimeric SMM Rungs. Molecules. 2021; 26(18):5626. https://doi.org/10.3390/molecules26185626

Chicago/Turabian Style

Arauzo, Ana, Elena Bartolomé, Javier Luzón, Pablo J. Alonso, Angelica Vlad, Maria Cazacu, Mirela F. Zaltariov, Sergiu Shova, Juan Bartolomé, and Constantin Turta. 2021. "Slow Magnetic Relaxation in {[CoCxAPy)] 2.15 H2O}n MOF Built from Ladder-Structured 2D Layers with Dimeric SMM Rungs" Molecules 26, no. 18: 5626. https://doi.org/10.3390/molecules26185626

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