A cyanide-bridged wheel featuring a seven-coordinate Mo(iii) center.

A new cyclic molecule incorporating [MoIII(CN)7]4- has been characterized by single crystal X-ray methods, SQUID magnetometry and theoretical calculations. The wheel molecule [MoIII(CN)7]6[Ni(L)]12(H2O)6 exhibits ferromagnetic Mo-Ni coupling which did not exist for the previously reported octacyanometallate analogue [MoIV(CN)8]6[Ni(L)]12(H2O)6. These results indicate that known supramolecular architectures incorporating octacyanometallates can be used as platforms for making new molecules incorporating seven-coordinate cyanide precursors.

Reversible On-Off Switching of a Single-Molecule Magnet via a Crystal-to-Crystal Chemical Transformation.

Dynamic molecular crystals are of high interest due to their potential applications. Herein we report the reversible on-off switching of single-molecule magnet (SMM) behavior in a [Mo(CN)] based molecular compound. Upon dehydration and rehydration, the trinuclear MnMo molecule [Mn(L)(HO)][Mo(CN)]·2HO (1) undergoes reversible crystal-to-crystal transformation to a hexanuclear MnMo compound [Mn(L)(HO)][Mn(L)][Mo(CN)] (2).

Three-Dimensional Fe-[Mo(CN)] Magnets with Ordering below 65 K and Distinct Topologies Induced by Cation Identity.

Two cyanide-bridged compounds based on the Fe cation and the anisotropic [Mo(CN)] anion, namely, {Fe(HO)[Mo(CN)]·5HO} (1) and {[NH(CH)]Fe(HO)[Mo(CN)]·8HO} (2), have been prepared. Single crystal X-ray analyses revealed that their structures exhibit different three-dimensional topologies as a result of the addition of [NH(CH)] during the synthesis of 2. For both 1 and 2, the geometry of the [Mo(CN)] unit is a slightly distorted capped trigonal prism; all Fe centers are hexacoordinate and adopt a distorted octahedral configuration.