{Mn^II₉W^V₆}_<i>n</i> Nanowires Organized into Three-Dimensional Hybrid Network of I¹O² Topology

Pentadecanuclear cyano-bridged high spin {MnII9WV6(CN)48(solv)24} clusters serve as bifunctional molecular building blocks in the construction of a {MnII9[WV(CN)8]6(dpe)5(MeOH)10}·14MeOH (dpe = trans-1,2-di(4-pyridyl)ethylene) organic−inorganic hybrid network of I1O2 topology. The intercluster connections are formed by Mn−NC−W and Mn−dpe−Mn linkages. The Mn−NC−W linkages lead to one-dimensional (1D) cyanido-bridged nanowires {Mn9W6}n with a van der Vaals diameter changing periodically from ∼1 to ∼1.5 Å, with Mn−dpe−Mn linkages controlling the effective distances between them. The magnetic measurements suggest the superparamagnetic behavior of {Mn9W6}n skeletons below 100 K due to the internal ferrimagnetic ordering through CN− bridges. Below 3.5 K, weak antiferromagnetic interactions between the {Mn9W6}n operate, with two inflection points H1 = 100 Oe and H2 = 480 Oe observed in the M(H) curve at 1.8 K.