Abstract
p-tBu-calix[4]arene (H4TBC[4]) has proven to be an incredibly versatile ligand for the synthesis of 3d- and 3d/4f- clusters, in particular those containing mixed-valent Mn ions. These are of interest to the magnetochemist for the diversity of magnetic behaviours that can be shown, along with a huge variety of nuclearities and topologies accessible, which allow one to outline magneto-structural correlations and a quantitative understanding of their properties. This contribution reports the synthesis, analysis and magnetic properties of a Brucite-like Mn-oxo/hydroxo octanuclear fragment encapsulated within/capped by four [MnIII-TBC[4]]− moieties. A diol coligand in the reaction mixture plays a seemingly important role in determining the outcome, though it is not incorporated in the final structure.
Highlights
Manganese continues to play a prominent role in the chemistry of 3d transition metals, owing to its significance across a breadth of research areas, including bioinorganic [1] and biomedicinal chemistry [2], catalysis [3], nanomaterials [4], spectroscopy [5], and molecular magnetism [6]
The ability of the Mn ion to exist in a variety of stable oxidation states (II-IV) allows for the construction of polymetallic cluster compounds exhibiting a variety of interesting magnetic behaviours, including the stabilization of large spin ground states [7], the slow relaxation of magnetization [8], spin frustration [9], vibrational coherences [10], and enhanced magnetocaloric effects [11]
A key component in understanding the physical properties of all Mn-based molecular magnets is the construction of large families of related compounds so that structure-magnetism relationships can be quantitatively rationalised, and this requires the careful design and exploitation of specific organic bridging ligands
Summary
Manganese continues to play a prominent role in the chemistry of 3d transition metals, owing to its significance across a breadth of research areas, including bioinorganic [1] and biomedicinal chemistry [2], catalysis [3], nanomaterials [4], spectroscopy [5], and molecular magnetism [6]. We have been exploring the coordination chemistry of calix[n]arenes (C[n]s) with Mn (as well as other metals), as these molecules hold the potential to isolate coordination clusters in the solid state in various different ways, for example, by exploiting the wedge shape of p-tBu-calix[4]arene (H4TBC[4]). As can be seen from the acetonitrile (CH3CN) solvate of H4TBC[4] (Figure 1a) [12], the shape of the building block exerts strong influence over assembly and typically results in antiparallel bilayer formation in the solid state.
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