Testing the High Spin MnII9WV6 Cluster as Building Block for Three-Dimensional Coordination Networks

Abstract

Pentadecanuclear high spin cyano-bridged {M' II 9 M v 6 (CN)48(solv)24) (M' = 3d metal ions; M = Mo, W; solv = H 2 O, alcohol) clusters are considered as building blocks for three-dimensional open networks. Self-assembly of Mn II 9 W v 6 clusters (S = 39/2) with 4,4'-bipyridine leads to their organization into an organic-inorganic hybrid coordination network {Mn II 9 (4,4'-bpy) 4 [W v (CN) 8 ] 6 (EtOH) 12 (H 2 O) 4 } ·10EtOH 1 (System, triclinic; space group: P1, a = 17.1569(2) A, b = 17.3835(2) A, c = 19.2530(2) A, a = 103.5520(10)°, P = 115.3950(10)°, y = 98.3060(10)°, Z = 1). The clusters are connected through 4,4'-bpy spacers into a two-dimensional square-grid coordination framework extended in the ab crystallographic plane with the smallest intercluster separation along the a (Mn···W = 7.12 A) and b (Mn···W = 7.15 A) directions significantly lower than that along the c crystallographic direction (Mn···W = 8.64 A). Direct current magnetic measurements suggest strong dominance of intracluster antiferromagnetic Mn II -W v coupling over a very weak intercluster antiferromagnetic interaction.