Cyano-bridged bimetallic assemblies from hexacyanometalate, [M(CN)6]3- (M = MnIII and FeIII), and [M(N4-macrocycle)]2+ (M = FeIII, NiII and ZnII) building blocks.: Syntheses, multidimensional structures, and magnetic properties

Reactions between [M(N-4-macrocycle)](2+) (M = Z(II) and N-II; macrocycle ligands are either CTH = d,1-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane or cyclam = 1,4, 8, 11 -tetrazaazaciclotetradecane) and [M(CN)(6)](3-) (M = Fe-III and Mn-III) give rise to cyano-bridged assemblies with 1D linear chain and 2D honeycomblike structures. The magnetic measurements on the 1D linear chain complex [Fe(cyclam)][Fe(CN)(6)]. 6H(2)O 1 points out its metamagnetic behavior, where the ferromagnetic interaction operates within the chain and the antiferromagnetic one between chains. The Neel temperature, T-N, is 5.5 K and the critical field at 2 K is 1 T. The unexpected ferromagnetic intrachain interaction can be rationalized on the basis of the axially elongated octahedral geometry of the low spin F-III ion of the [Fe(cyclam)](3+) unit. The isostructural substitution of [Fe(CN)6](3-) [Mn(CN)(6)](3-) in the previously reported complex [Ni(cyclam)](3)[Fe(CN)(6)](2). 12H(2)O 2 leads to [Ni(cyclam)](3)[Mn(CN)(6)](2). 16 H2O 3, which exhibits a corrugated 2D honeycomblike structure and a metamagnetic behavior with T-N = 16 K and a critical field of 1 T. In the ferromagnetic phase (H > 1 T) this compound shows a very important coercitive field of 2900 G at 2 K. Compound [Ni(CTH)](3)[Fe(CN)(6)](2). 13H(2)O 4, C60H116FE2N24Ni3O13, monoclinic, A 2/n, a = 20.462(7), b = 16.292(4), c = 27.262(7) Angstrom, beta = 101.29(4)degrees, Z = 4, also has a corrugated 2D honeycomblike structure and a ferromagnetic intralayer interaction, but, in contrast to 2 and 3, does not exhibit any magnetic ordering. This fact is likely due to the increase of the interlayer separation in this compound. {[Zn(cyclam)Fe(CN)(6)Zn(cyclam)] [Zn(cyclam)Fe(CN)(6)]. 22H(2)O-EtOH} 5, C44H122Fe2N24O23Zn3, monoclinic, A 2/n, a = 14.5474(11), b = 37.056(2), c = 14.7173(13) Angstrom, beta = 93.94(1)degrees, Z = 4, presents an unique structure made of anionic linear chains containing alternating [Zn(cyclam)](2+) and [Fe(CN)(6)](3-) units and cationic trinuclear units [Zn(cyclam)Fe(CN)(6)Zn(cyclam)](+). Their magnetic properties agree well with those expected for two [Fe(CN)(6)](3-) units with spin-orbit coupling effect of the low spin iron(III) ions.