A comparative structural and magnetic study of three compounds based on the cluster unit M4Cl8(THF)(6) (M = Mn, Fe, Co)

Treatment of anhydrous MCl2, phases with THF under refluxing conditions lea ds to excision of the clusters M4Cl8(THF)(6) (M = Fe (1), Co (3)) and dimen sional reduction to the chain of clusters, {Mn4Cl8(THF)(6)(Mn(THF)(2)Cl-2}( infinity), (2), All three compounds were isolated in high yields as crystal line materials and subjected to comprehensive magnetic studies. X-ray struc tures of the three compounds were performed to verify the nature of the com pounds, but only the Mn derivative is discussed in detail due to the fact t hat the structures of the Fe and Co clusters were reported earlier. The mol ecular structures of M4Cl8(THF)(6) (M = Fe, Co) consist of a rhombic arrang ement of metal ions with two octahedral and two pseudo-five-coordinate meta l sites, The four outer edges of the cluster are each spanned by a chloride bridge, while the short diagonal is bridged by two chloride ions. The rema inder of the coordination sites are occupied by two terminal chlorides and six THF solvent molecules, The 1D compound {Mn4Cl8(THF)(6)(Mn(THF)(2)Cl-2}( infinity), (2), is related to (1) and (3) in that the core of the structure is the same, but in this case the M4Cl8(THF)(6) units are linked by MnCl2( THF)(2) bridges. The magnetic susceptibility data for Fe4Cl8(THF)(6) (1) an d Co4Cl8(THF)(6) (3) in the high-temperature range are indicative of the pr esence of ferromagnetic and antiferromagnetic interactions respectively. Fi tting of the data to anisotropic exchange models provided information on th e intramolecular exchange parameters. In the low-temperature region, cooper ative behavior was observed as a consequence of the presence of significant intercluster interactions, The Fe derivative behaves as a metamagnet, whil e the Co derivative is a weak ferromagnet below 3.5 K, In contrast to (1) a nd (3), the magnetic properties of {Mn4Cl8(THF)(6)(Mn(THF)(2)Cl-2}(infinity ) (2), are indicative of the presence of antiferromagnetic exchange interac tions within the cluster as well as between the neighboring clusters that l ead to a nonmagnetic ground state. (C) 2001 Academic Press.