Use of a rhenium cyanide nanomagnet as a building block for new clusters and extended networks

Derivatives of the single molecule magnet (SMM) {[Re(triphos)(CN)3]4[MnCl]4} (Re4Mn4) {[Re(triphos)(CN)3]4[Mn(CH3CN)]4}(ClO4)4 (2) and {[Re(triphos)(CN)3]4[Mn(ClO4)]3[Mn(CH3OH)(CH3O)]} (3), were prepared by reacting [Et4N][Re(triphos)(CN)3] (1) with Mn(ClO4)2·6H2O. Reaction of sodium dicyanamide, NaN(CN)2, with compound 2 in CH2Cl2 results in the product {[Re(triphos)(CN)3]4[Mn(N(CN)2)]4} (4), in which each Mn(II) site is terminated by a dicyanamide ligand. A similar reaction of compound 3 in CH2Cl2–MeOH solution with LiTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) leads to the formation of {[Re(triphos)(CN)3]4[Mn(TCNQ-TCNQ)3(Mn(HTCNQ)(CH3O))]} (5) whose structure is best described as a chain of dimers of Re4Mn4 cubes bridged by σ-bonded (TCNQ2)2− linkers with one capping HTCNQ ligand.