Synthesis and characterisation of a Ni4 single-molecule magnet with S4 symmetry

Alan Ferguson; Jon Lawrence; Andrew Parkin; Javier Sanchez-Benitez; Konstantin V. Kamenev; Euan K. Brechin; Wolfgang Wernsdorfer; Stephen Hill; Mark Murrie

doi:10.1039/B807447J

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Dalton Transactions

Issue 45, 2008

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Synthesis and characterisation of a Ni₄ single-molecule magnet with S₄ symmetry

Alan Ferguson , Jon Lawrence , Andrew Parkin , Javier Sanchez-Benitez , Konstantin V. Kamenev , Euan K. Brechin , Wolfgang Wernsdorfer , Stephen Hill and Mark Murrie

Dalton Trans., 2008, 6409-6414

DOI: 10.1039/B807447J
Received 02 May 2008, Accepted 15 Aug 2008
First published on the web 08 Oct 2008

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Abstract
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[Ni₄Cl₄(HL)₄] (1) {H₂L [double bond, length as m-dash] HN(CH₂CH₂OH)₂} has S₄ symmetry and crystallises in the tetragonal space group I4₁/a. Two exchange couplings are observed between the four Ni(II) centres, with J1 = 7.29 cm⁻¹ and J2 = −2.08 cm⁻¹, leading to an S = 4 ground state. The Ni₄ complex shows the onset of frequency dependent signals in the out-of-phase ac susceptibility below 3 K. In single-crystal measurements carried out using a micro-SQUID, hysteresis loops are observed below 0.5 K, confirming that 1 shows slow relaxation of magnetisation. The loops are temperature dependent but only weakly sweep rate dependent due to the presence of small intermolecular interactions, which hinder quantum tunnelling. This exchange bias between Ni₄ molecules is also seen in high-frequency high-field EPR measurements, which give the parameters D = −0.75 cm⁻¹, B₄° = −6.7 × 10⁻⁵ cm⁻¹ and g_z = 2.275.

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Alan Ferguson
Jon Lawrence
Andrew Parkin
Javier Sanchez-Benitez
Konstantin V. Kamenev
Euan K. Brechin
Wolfgang Wernsdorfer
Stephen Hill
Mark Murrie

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Dalton Transactions

Synthesis and characterisation of a Ni₄ single-molecule magnet with S₄ symmetry

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