Supramolecular Entanglement from Interlocked Molecular Nanomagnets

The trinuclear nanomagnet [Mn III 3 O(Et-sao) 3 (MeOH) 3 ](ClO 4 ) ( 1 ) has been utilized as a building block for the construction of the hexanuclear cluster [{Mn III 3 O(Et-sao) 3 (O 2 CPh)(EtOH)} 2 {4,4′-bpe} 2 ] ( 3 ) that conforms to a rectangle and the two-dimensional coordination polymer {[Mn III 3 O(sao) 3 (4,4′-bpe) 1.5 ]ClO 4 ·3MeOH} n ( 2 ·3MeOH). The latter exhibits an unprecedented type of entanglement that is based on host guest interactions. The polygon versus the polymer is rationalized in terms of changing an auxiliary anion that influences the arrangement of the potentially “vacant” coordination axes on each Mn III ion of the trinuclear precursor and thereby directing the self-assembly process.