4.7 Article

Synthesis and characterisation of a Ni(4) single-molecule magnet with S(4) symmetry

Journal

DALTON TRANSACTIONS
Volume -, Issue 45, Pages 6409-6414

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/b807447j

Keywords

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Funding

  1. University of Glasgow
  2. EPSRC
  3. University of Florida is supported by the US National Science Foundation [DMR0239481, 0506946]
  4. EPSRC [EP/E06471X/1, EP/D503744/1] Funding Source: UKRI
  5. Engineering and Physical Sciences Research Council [EP/E06471X/1, GR/T20762/01, EP/D503744/1] Funding Source: researchfish

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[Ni(4)Cl(4)(HL)(4)] (1) {H(2)L=HN(CH(2)CH(2)OH)(2)} has S(4) symmetry and crystallises in the tetragonal space group I4(1)/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 Ni(4) 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), B(4)degrees = -6.7 x 10(-5) cm(-1) and g(z) = 2.275.

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