Octacyanometalate Networks

Treatment of several binary transition metal p-toluenesulfonates (M^II(OTs)₂) with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [M^II(DMF)₄]₃[M^V(CN)₈]₂ (M^V = Mo, W; M^II = Mn, Fe, Ni) stoichiometry. Magnetic measurments indicate that the 2-D lattices are ferrimagnets (Mn^II) while 1-D derivatives do not exhibit long-range magnetic ordering. Truncated structures of the networks are illustrated below in Figure 6.

Poly(pyrazolyl)borate Tricyanide Networks

Treatment of [NEt₄][Tp*Fe^III(CN)₃] with manganese(II) triflate in DMF affords rectangular clusters while tosylate salts afford one-dimensional networks via in situ trapping of the cationic {[Tp*Fe^III(CN)(m-CN)₂Mn^II]}²⁺ cluster (Scheme 4).

The one-dimensional chain of squares network appears to be derived from {cis-(m-O₃SC₆H₄Me)₂Mn^II(DMF)₄}_n (Figure 7), which is obtained via crystallization of Mn(OTs)₂ from DMF/Et₂O mixtures. Magnetic studies suggest that antiferromagnetic exchange between Mn^II and Fe^III centers is present, the Tp*Fe^III(CN)₃^- centers are highly anisotropic, and that bridging tosylates are poor superexchange pathways.

We are currently exploring the preparation of networks absent of tosylate anions. We anticipate that judicious choice of transition metal centers will afford several interesting magnetic and photomagnetic lattices.