Enhanced ion anisotropy by nonconventional coordination geometry: single-chain magnet behavior for a [{Fe(II)L}2{Nb(IV)(CN)8}] helical chain compound designed with heptacoordinate Fe(II).

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {Fe(II)Nb(IV)} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb(IV), Mo(IV), W(IV)). X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H(2)O)Fe(L(1))}{M(CN)(8)}{Fe(L(1))}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L(1))}(2+) and {M(CN)(8)}(4-) units (L(1) stands for the pentadentate macrocycle).

Tetranuclear [{Ni(HL3)}{W(CN)8}]2 square: a case of antiferromagnetic {NiIIWV} interactions.

A tetranuclear cyano-bridged [{Ni(HL3)}{W(CN)8}]2 compound in a square geometry was formed by self-assembling of {W(CN)8}3- and {NiL3}2+ (L3=pentadentate ligand). The structure of the compound has been established by single crystal X-ray diffraction. The coordination sphere of the Ni ions is severely distorted with the macrocyclic ligand adopting a facial coordination with only four linkages to the metal center.

Synthesis, crystal structure, and magnetic properties of hexanuclear [{MnL2}4{Nb(CN)8}2] and Nonanuclear [{MnL2}6{Nb(CN)8}3] heterometallic clusters (L=bpy, phen).

A hexanuclear cyano-bridged {MnII4NbIV2} cluster (1) bearing 2,2'-bipyridine (bpy) as the blocking ligand at manganese is obtained from the reaction of cis-[MnCl2(bpy)2] and K4[Nb(CN)8]. When the blocking ligand is 1,10-phenanthroline (phen), a nonanuclear cluster {MnII6NbIV3} (2) is obtained. The structure of [{Mn(bpy)2}4{Nb(CN)8}2] has been solved by single-crystal X-ray crystallography, whereas the phen derivative has been confirmed by means of the structure analysis of the corresponding WIV analogue [{Mn(phen)2}6{W(CN)8}3(H2O)2].