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Issue 20, 2010
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A Mn15 single-molecule magnet consisting of a supertetrahedron incorporated in a loop

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Abstract

Two new Mn15 clusters consisting of a supertetrahedron which is incorporated in a loop are reported. The reactions of [Mn(O2CEt)2]·2H2O with the diols 1,3-propanediol (H2pd) or 2-methyl-1,3-propanediol (H2mpd) in the presence of KX (X = CN, Cl, Br, NO3, ClO4, OCN, SCN) afforded compounds [Mn15K(μ4-O)4(O2CEt)11(pd)12(py)2] (1) and [Mn15K(μ4-O)4(O2CEt)11(mpd)12(py)2] (2). The structural core of 1 and 2 consists of a Mn11 loop and a Mn9K supertetrahedron sharing a Mn5 triangle. To the best of our knowledge, the structural motif of a supertetrahedron incorporated in a loop appears for the first time in metal cluster chemistry. Variable-temperature, solid-state direct current (dc) magnetic susceptibility studies in the 300–5 K range showed that the χMT value increases with decreasing T suggesting the existence of predominant ferromagnetic exchange interactions and a relatively large ground state spin. This was confirmed by field-variable temperature magnetization measurements which were fitted using a matrix diagonalization method to give S∼ 23/2, g = 1.92(1) and D = −0.071(2) cm−1. In addition, compound 1 displays frequency-dependent alternating current (ac) signals suggesting single-molecule magnetism (SMM) behaviour. This was proven by magnetization vs. dc field sweeps on single-crystals of 1·0.7py·1.3MeCN, which displayed sweep rate- and temperature-dependent hysteresis loops.

Graphical abstract: A Mn15 single-molecule magnet consisting of a supertetrahedron incorporated in a loop

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Publication details

The article was received on 04 Jan 2010, accepted on 14 Apr 2010 and first published on 26 Apr 2010


Article type: Paper
DOI: 10.1039/B927205D
Citation: Dalton Trans., 2010,39, 4978-4985
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    A Mn15 single-molecule magnet consisting of a supertetrahedron incorporated in a loop

    E. E. Moushi, A. Masello, W. Wernsdorfer, V. Nastopoulos, G. Christou and A. J. Tasiopoulos, Dalton Trans., 2010, 39, 4978
    DOI: 10.1039/B927205D

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