Slow relaxation in a {Tb 2 Ba(&alpha;-fur) 8 } :N polymer with Ln = Tb(iii) non-Kramers ions

Bartolome Bartolome; Arauzo A.; Luzon Javier; Melnyk Silvia; Shova Sergiu; Prodius Denis; Bartolome Juan; Amann Andreas; Nallaiyan Manivannan; Spagna Stefano

Conţinutul numărului revistei

Articolul precedent

Articolul urmator

952

SM ISO690:2012

BARTOLOME, Bartolome, ARAUZO, A., LUZON, Javier, MELNYK, Silvia, SHOVA, Sergiu, PRODIUS, Denis, BARTOLOME, Juan, AMANN, Andreas, NALLAIYAN, Manivannan, SPAGNA, Stefano. Slow relaxation in a {Tb 2 Ba(α-fur) 8 } :N polymer with Ln = Tb(iii) non-Kramers ions. In: Dalton Transactions, 2019, nr. 15(48), pp. 5022-5034. ISSN 1477-9226. DOI: https://doi.org/10.1039/c8dt05044a

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Dalton Transactions

Numărul 15(48) / 2019 / ISSN 1477-9226 /ISSNe 1477-9234

Slow relaxation in a {Tb ₂ Ba(α-fur) ₈ } _:N polymer with Ln = Tb(iii) non-Kramers ions

DOI:https://doi.org/10.1039/c8dt05044a

Pag. 5022-5034

Bartolome Bartolome¹, Arauzo A.², Luzon Javier²³, Melnyk Silvia⁴⁵, Shova Sergiu⁶, Prodius Denis⁵⁴, Bartolome Juan², Amann Andreas⁷, Nallaiyan Manivannan⁷, Spagna Stefano⁷

¹ Escola Universitària Salesiana de Sarrià (EUSS), Barcelona,
² Universidad de Zaragoza,
³ Centro Universitario de la Defensa, Academia General Militar, Zaragoza,
⁴ Institute of Chemistry,
⁵ Academy of Sciences of Moldova,
⁶ “Petru Poni” Institute of Macromolecular Chemistry,
⁷ Quantum Design Inc.

Disponibil în IBN: 20 aprilie 2019

Rezumat

We report the synthesis, crystal structure and magnetic properties of a new heteronuclear polymeric complex based on non-Kramers Tb ions and carboxylic α-fur = C ₄ H ₃ OCOO ligands: {[Tb ₂ Ba(α-fur) ₈ (H ₂ O) ₄ ]·2H ₂ O} _n . The α-furoate ligands consolidate 1D zig-zag chains running along the c-axis, formed by Tb ₂ dimers separated by Ba ions. Ab initio calculations, in combination with the fit of experimental data, predict that the single-ion magnetic ground state is highly anisotropic and consists of a quasi-doublet with a Δ _Tb /k _B = 3.22 K gap, well separated from the next excited state, while the gap for the Tb ₂ dimer is Δ _2Tb /k _B = 2.58 K. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as dimers of non-Kramers Tb ions, coupled by an antiferromagnetic intradimer interaction J′∗/k _B = -1.6 K. Dipolar interactions couple the Tb ions in the dimer with their first neighbour ions along the chain, with J′′∗/k _B = -0.15 K, and with the surrounding ions out of the chain, with maximum J′′′∗/k _B = -0.03 K. Ac susceptibility measurements in H = 0 performed down to 50 mK temperatures have enabled us to observe slow relaxation of magnetization, with an Orbach-like activation energy of U/k _B = 1.1 K. It is assigned to the sluggish response of the 3D spin system due to a short-range ordering, possibly enhanced by the presence of disorder caused by defects in the polymeric chains. Under the application of a magnetic field, the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect. We discuss the different relaxational phenomenology of the new complex in comparison with that of the isostructural {[Dy ₂ Ba(α-fur) ₈ (H ₂ O) ₄ ]·2H ₂ O} _n , differing only in the Kramers nature of the ions, and the mononuclear {Ln(α-fur) ₃ (H ₂ O) ₃ } _n (Ln = Tb, Dy) complexes, previously reported.

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<cfAbstr cfLangCode='EN' cfTrans='o'><p>We report the synthesis, crystal structure and magnetic properties of a new heteronuclear polymeric complex based on non-Kramers Tb ions and carboxylic &alpha;-fur = C <sub>4</sub> H <sub>3</sub> OCOO ligands: {[Tb <sub>2</sub> Ba(&alpha;-fur) <sub>8</sub> (H <sub>2</sub> O) <sub>4</sub> ]&middot;2H <sub>2</sub> O} <sub>n</sub> . The &alpha;-furoate ligands consolidate 1D zig-zag chains running along the c-axis, formed by Tb <sub>2</sub> dimers separated by Ba ions. Ab initio calculations, in combination with the fit of experimental data, predict that the single-ion magnetic ground state is highly anisotropic and consists of a quasi-doublet with a &Delta; <sub>Tb</sub> /k <sub>B</sub> = 3.22 K gap, well separated from the next excited state, while the gap for the Tb <sub>2</sub> dimer is &Delta; <sub>2Tb</sub> /k <sub>B</sub> = 2.58 K. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as dimers of non-Kramers Tb ions, coupled by an antiferromagnetic intradimer interaction J&prime;&lowast;/k <sub>B</sub> = -1.6 K. Dipolar interactions couple the Tb ions in the dimer with their first neighbour ions along the chain, with J&prime;&prime;&lowast;/k <sub>B</sub> = -0.15 K, and with the surrounding ions out of the chain, with maximum J&prime;&prime;&prime;&lowast;/k <sub>B</sub> = -0.03 K. Ac susceptibility measurements in H = 0 performed down to 50 mK temperatures have enabled us to observe slow relaxation of magnetization, with an Orbach-like activation energy of U/k <sub>B</sub> = 1.1 K. It is assigned to the sluggish response of the 3D spin system due to a short-range ordering, possibly enhanced by the presence of disorder caused by defects in the polymeric chains. Under the application of a magnetic field, the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect. We discuss the different relaxational phenomenology of the new complex in comparison with that of the isostructural {[Dy <sub>2</sub> Ba(&alpha;-fur) <sub>8</sub> (H <sub>2</sub> O) <sub>4</sub> ]&middot;2H <sub>2</sub> O} <sub>n</sub> , differing only in the Kramers nature of the ions, and the mononuclear {Ln(&alpha;-fur) <sub>3</sub> (H <sub>2</sub> O) <sub>3</sub> } <sub>n</sub> (Ln = Tb, Dy) complexes, previously reported.</p></cfAbstr>
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