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Calix[4]arenes are versatile ligands that, whilst also serving other purposes, can act as platforms for the synthesis of a wide range of 3 d, 4 f, and 3 d-4 f polymetallic clusters. The empirical metal ion binding rules established for calix[4]arene are closely mirrored by bis-calix[4]arene, a relatively new ligand in which two equivalents of the former are directly tethered at a methylene bridge position. The direct tethering within bis-calix[4]arene gives rise to some structural features that are related to calix[4]arene coordination chemistry, but the prevailing clusters have fascinating new topologies and coordination behaviors. Here, we present the synthesis of a family of new bis-calix[4]arene-supported 3 d-4 f clusters, as well as their structural characterization and magnetic properties. Comparison is drawn with calix[4]arene coordination chemistry, showing logical extension of common structural fragments and cluster capping behaviors upon moving to bis-calix[4]arene. This approach therefore holds great potential for tuning cluster formation and composition at a high level through subsequent ligand alteration. [ABSTRACT FROM AUTHOR]

Calix[4]arenes are versatile ligands capable of forming a wide range of cluster motifs when reacted with 3d, 4for 3d/4fmetal ions. Synthetic modification at the calix[4]arene methylene bridge offers a unique opportunity to explore cluster formation with these alternative building blocks. Here, we present the synthesis of a range of bis-calix[4]arenes that are tethered by alkyl chains, as well as exploratory structural studies into cluster-forming reactions. Single crystals were formed in four cases, and from the X-ray structures elucidated it is possible to conclude that sufficiently long alkyl tethers allow for the formation of established cluster topologies without disruption to the core coordination chemistry. Synthetic modification at the calix[4]arene methylene bridge offers a unique opportunity to synthesise alternative supramolecular building blocks. This paper describes the synthesis of a range of alkyl-tethered bis-calix[4]arenes, as well as exploratory structural studies into polymetallic cluster formation. [ABSTRACT FROM AUTHOR]

The central MnII ions in a series of calix[4]arenestabilised butterflies can be sequentially replaced with LnIII ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of MnII for GdIII allows for the examination of the transferability of spin-Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low-lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single-ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TMII/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p-tBu-calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different "guests" within structurally robust "hosts". [ABSTRACT FROM AUTHOR]

Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3 d-4 f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures. [ABSTRACT FROM AUTHOR]

A bis-phenolate that has structural similarities to both calix[4]arene and the oxacalix[ n]arenes provides access to a 'butterfly'-like Mn4 cluster in which all metals are in the oxidation state+3. Specific properties of this ligand, in comparison to others in the literature, offer a route to influencing the orientation of the Jahn-Teller axes within this cluster motif, which possesses a rare oxidation state arrangement. [ABSTRACT FROM AUTHOR]

Abstract: Methylene-bridged calix[4]arenes have emerged as excellent ligands for polynuclear cluster formation. In this contribution methylene- and oxa-bridged calix[6]arenes have been examined as candidates for cluster formation with cobalt(II) nitrate, affording two markedly different structures. The nature of the structures is highly dependent on the bridging atoms. Reaction of p-tert-butylcalix[6]arene with cobalt(II) nitrate in DMF results in the formation of a coordination polymer in which the calixarene adopts a ‘double-partial’ cone conformation. A similar reaction with p-tert-butyltetrahomodioxacalix[6]arene affords a discrete complex in which a central heteroatom also coordinates to the metal centre, with the calixarene in a ‘double-cone’ conformation. The synthesis and structure of both compounds is presented. [Copyright &y& Elsevier]

Abstract: Methylene-bridged calix[4]arenes have emerged as excellent ligands for polynuclear cluster formation. In this contribution methylene- and oxa-bridged calix[6]arenes have been examined as candidates for cluster formation with cobalt(II) nitrate, affording two markedly different structures. The nature of the structures is highly dependent on the bridging atoms. Reaction of p-tert-butylcalix[6]arene with cobalt(II) nitrate in DMF results in the formation of a coordination polymer in which the calixarene adopts a ‘double-partial’ cone conformation. A similar reaction with p-tert-butyltetrahomodioxacalix[6]arene affords a discrete complex in which a central heteroatom also coordinates to the metal centre, with the calixarene in a ‘double-cone’ conformation. The synthesis and structure of both compounds is presented. [Copyright &y& Elsevier]

Supramolecular Chemistry In the Full Paper on page 2804 ff., S. Piligkos, E. K. Brechin, S. J. Dalgarno et al. report the use of methylene ‐ bridged calix[4]arenes as versatile ligand supports for the construction of polymetallic clusters with fascinating magnetic properties. Empirical metal ‐ ion binding rules established for this building block help to partially rationalise the complex assembly process. Linking calix[4]arenes at the methylene bridge provides improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis ‐ calix[4]arenes and transition metal ions or 3d ‐ 4f combinations display characteristic features of the analogous calix[4]arene ‐ supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures. [ABSTRACT FROM AUTHOR]