Pentanuclear [2.2] spirocyclic lanthanide(III) complexes: slow magnetic relaxation of the DyIII analogue

Sourav Biswas; Sourav Das; Jan van Leusen; Paul Kögerler; Vadapalli Chandrasekhar

doi:10.1039/C5DT03060A

Pentanuclear [2.2] spirocyclic lanthanide(iii) complexes: slow magnetic relaxation of the Dy^III analogue†

Sourav Biswas,^a Sourav Das,^ab Jan van Leusen,^c Paul Kögerler*^c and Vadapalli Chandrasekhar*^ad

* Corresponding authors

^a Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India
E-mail: vc@iitk.ac.in, paul.koegerler@ac.rwth-aachen.de
Web: http://www.iitk.ac.in

^b Department of Emerging Materials Science, DGIST, Daegu 711-873, Korea

^c Institut für Anorganische Chemie, RWTH Aachen University, D-52074 Aachen, Germany
Web: http://www.ac.rwth-aachen.de

^d National Institute of Science Education and Research, Sachivalaya Marg, PO: Sainik School, Bhubaneswar-751 005, India
Web: http://www.niser.ac.in

Abstract

The reaction of LnCl₃·6H₂O (Ln = Dy³⁺, Tb³⁺ and Ho³⁺) with the multisite coordinating ligand N′-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylidene)acetohydrazide (LH₃) in the presence of pivalic acid (PivH) leads to the formation of three isostructural homometallic pentanuclear complexes, [Dy₅(LH)₄(η¹-Piv)(η²-Piv)₃(μ₂–η²η¹Piv)₂(H₂O)]·Cl·9·5H₂O·5MeOH (1), [Tb₅(LH)₄(η¹-Piv)(η²-Piv)₃(μ₂–η²η¹Piv)₂(H₂O)]·Cl·10.5H₂O·2MeOH·2CHCl₃ (2) and [Ho₅(LH)₄(η¹-Piv)(η²-Piv)₃(μ₂–η²η¹Piv)₂(H₂O)]·Cl·14.5H₂O·2CHCl₃ (3). 1–3 are monocationic and are comprised of four doubly deprotonated [LH]²⁻ ligands along with six pivalate ions. These complexes possess a [2.2] spirocyclic topology formed by the fusion of two triangles of Ln^III ions at a common vertex. The magneto chemical analysis reveals the presence of antiferromagnetic exchange interactions at low temperature, and the Dy^III complex 1 gives an out-of-phase signal with a small curvature in alternating current (ac) magnetic susceptibility measurement. Application of a 3000 G static field during ac measurement intensifies the signals, revealing a second slow relaxation process in the Dy^III analogue.

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Article information

DOI: https://doi.org/10.1039/C5DT03060A
Article type: Paper
Submitted: 08 Aug 2015
Accepted: 04 Oct 2015
First published: 07 Oct 2015
This article is Open Access

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Dalton Trans., 2015,44, 19282-19293

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Pentanuclear [2.2] spirocyclic lanthanide(III) complexes: slow magnetic relaxation of the Dy^III analogue

S. Biswas, S. Das, J. van Leusen, P. Kögerler and V. Chandrasekhar, Dalton Trans., 2015, 44, 19282 DOI: 10.1039/C5DT03060A

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