Spin-glass state in Ni5(OH)6(CnH2n−4O4)2 metal-organic frameworks (n = 6, 8, 10, 12)

•New members of the Ni5(OH)6(CnH2n−4O4)2 series with n = 10 and n = 12.•Synthesis by controlled mixing of reactants followed by hydrothermal treatment.•Spin-glass state below 19 K in Ni5(OH)6(CnH2n−4O4)2 series.

We present an extension of a previously published work (J. Solid State Chem. 181 (2008) 3229) concerning Metal-Organic Frameworks (MOFs) of general formula Ni5(OH)6(CnH2n−4O4)2. A modified synthesis procedure comprising a room-temperature step prior to the hydrothermal treatment was employed. This preliminary step made use of peristaltic pumps allowing slow mixing of the reactants at a constant pH value. Samples of better purity and crystallinity were consequently obtained. In particular, the better crystallinity allowed us to work on two other members of the series, n = 10 and n = 12, which were characterized using synchrotron powder X-ray powder diffraction. These two compounds are isoreticular with the n = 6 and n = 8 compounds previously reported. The crystal structure incorporates the long alkane dioic acid molecules as pillars between complex inorganic layers. Samples of better purity for n = 6 and 8, as well as those of the new compounds with n = 10 and 12, gave us the opportunity to revise the magnetic properties of these MOFs. We found similar magnetic behaviors, independently of the interlayer spacing. We show that, below 19 K, these materials most probably enter a spin-glass or cluster spin-glass state rather than a three-dimensionally long-range ordered state. We link this behavior to the complex topology of the magnetic exchange interactions within the inorganic layers which is very likely to be source of magnetic frustration.

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