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Unusual undecanuclear heterobimetallic Zn4Ln7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen

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Abstract

The synthesis, characterization and properties of two unprecedented undecanuclear heterobimetallic Zn4Ln7 complexes of formula [Zn4Ln7(L)8(O2)2(OH)4(Cl)4(H2O)4]·Cl·4H2O·4CH3CN (Ln = Gd (1), Dy (2)) encapsulating two peroxide anions are presented, representing a very rare example of a 3d-peroxo-Ln system and expanding the realm of metal-peroxo complexes. These eleven metal ions are arranged in a peculiar structural motif, where Zn4 is located at the peripheral shell wrapping Ln7 in the inner core. The Zn ions are penta-coordinate in all cases, linked to the NO2 donor atoms from the L2− ligand and to a hydroxyl group, and the apical position is occupied by a chloride anion. All LnIII ions in these systems are octa-coordinate with LnO8 and LnNO7 coordination spheres. Magnetocaloric effect (MCE) behavior has been found in the Gd analogue due to multiple low lying excited states arising from antiferromagnetic Gd–Gd exchange interactions. The Dy derivative shows frequency dependent out-of-phase signals indicating the presence of slow relaxation of magnetization below 8 K under zero applied direct current (dc) field, but without reaching a maximum, which is due to a faster quantum tunneling relaxation. The effective barrier extracted from the frequency dependent data is Ueff = 11.2 K and a τ0 of 4.18 × 10−6 s.

Graphical abstract: Unusual undecanuclear heterobimetallic Zn4Ln7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen

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Publication details

The article was received on 26 Apr 2017, accepted on 29 May 2017 and first published on 13 Jun 2017


Article type: Paper
DOI: 10.1039/C7DT01501A
Citation: Dalton Trans., 2017, Advance Article
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    Unusual undecanuclear heterobimetallic Zn4Ln7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen

    H. Ke, X. Lu, W. Wei, W. Wang, G. Xie and S. Chen, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT01501A

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