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

Abstract

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.