Abstract
Calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3d, 4f or 3d-4f metal ions. Calixarene-based metal ion fragments act as both bridging and structure capping moieties in these systems, and this behaviour is systematically extended upon moving to bis-calix[4]arene, a relatively new ligand in which two calix[4]arenes are tethered at the methylene bridge position. N,O-Ligands greatly influence cluster formation with bis-calix[4]arene, affording a remarkable mixed-valence [MnMnMn] cluster that displays coordination chemistry typical of each ligand type, but also new structure capping behaviour for the latter.
Highlights
Calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3d, 4f or 3d-4f metal ions
These molecules (e.g. p-tBu-calix[4]arene and p-H-calix[4]arene, hereafter collectively termed H4C[4]s) have emerged as versatile platforms for the synthesis of polymetallic clusters, capable of affording a wide variety of different structural topologies depending on the nature of the metal ions present; markedly different structures result from the incorporation of 3d,3 4f,4 or 3d and 4f metal ions
With respect to the present contribution, noteworthy systems resulting from these studies include a family of [MnIII2MnII2(C[4])2] single molecule magnets3b,c (SMMs, 2, Fig. 1B) that feature the aforementioned butterfly-like cluster; in this case the oxidation state distribution is the reverse of those reported in the literature for other ligand types
Summary
Calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3d, 4f or 3d-4f metal ions.
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