Anionic dicyanamide frameworks as possible components of multifunctional materials

The dicyanamide anion, [N(CN)2] – (hereafter abbreviated dca), has been shown to be a versatile building block for the assembly of coordination polymers which are components of molecular superconductors, magnets and conducting/magnetic hybrid materials. Significantly different anion topologies have been observed. We report the first study of the use of alkylammonium cations as templates for [M(dca)3] – (M = Mn and Ni) anionic networks, including a novel three-dimensional anionic structure in the (Bu3NH)4[Mn3(dca)10] salt. The molecular superconductors with the highest superconducting transition temperature, -(ET)2[Cu(dca)X] [X = Cl, Br; ET, commonly abbreviated as BEDT-TTF, is bis(ethylenedithio)tetrathiafulvalene] contain chains of diamagnetic Cu(I) ions linked by dca anions. The successful introduction of magnetically active transition metals into the charge-compensating dca layer will also be discussed. Specifically, we have synthesized and characterized the (ET)2[Mn(dca)3] salt that contain a novel triangular, spin frustrated, anion lattice separated by conducting layers of ET radical cations.