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A unique case of a grid-of-mesocates sequentially assembled by supramolecular cobalt(ii) meso-helical units connected through hydrogen bonding is reported. [ABSTRACT FROM AUTHOR]

A method to modulate the strength of the superexchange coupling interaction in dinuclear helical assemblies based on the coordination preferences of the metal centres is described. [ABSTRACT FROM AUTHOR]

Abstract: A series of Mn(III) nitrate complexes have been synthesized from dianionic hexadentate Schiff bases obtained by condensation of 3-methoxy-2-hydroxybenzaldehyde with different diamines. The complexes have been characterised by elemental analysis, ESI mass spectrometry, IR and 1H NMR spectroscopy. Magnetic studies and molar conductivity measurements were also performed. Complexes [MnL1(H2O)2]2·2NO3·2CH3OH (1), [MnL2(H2O)2]2·2NO3·2CH3OH (2) and [MnL5(H2O)2]2·2NO3·6H2O (5) were crystallographically characterised. The X-ray structures show an octahedral geometry around the metal with the Schiff base in the equatorial plane acting as tetradentate and water or methanol molecules in the axial positions. The octahedron entities are linked in pairs by μ-aquo bridges between neighbouring axial water molecules and also by π–π stacking interactions, establishing dimeric and polymeric structures. Nitrate anions are accommodated in the cavities of the framework and form hydrogen bonds with the aqua ligands and the methanol or crystal water, leading to infinite supramolecular aggregates of the complexes. Comparison of chloride, perchlorate and nitrate complexes indicate that the nature of the anions is the key factor directing the structural topologies. [Copyright &y& Elsevier]

The ability to organize functional molecules into higher dimensional arrays with well-defined spatial relationships between the components is one of the major goals in supramolecular chemistry. We report here a new route for the preparation of supramolecular boxes, incorporating two types of metal ions: (i) alkali-metal ions, which induce the supramolecular architecture and essentially play a structural role in the final compounds; (ii) manganese(III) ions, which are redox-active systems and give functionality to the new cages. Our results evidence that the size of the cavity inside the box can be tuned depending on the alkali metal used, a characteristic that gives this new family of compounds the potential to act selectively against different substrates. These compounds behave as active catalysts for disproportionation of H2O2 or for water photolysis, but they catalyze neither catecholase reaction nor peroxidase action upon using bulky organic substrates. [ABSTRACT FROM AUTHOR]