Abstract

The direct redox reaction between tetracyanoethylene (TCNE) and a planar porphyrinatomanganese(II), octakis(2,3,7,8,12,13,17,18-methylthio)porphyrinatomanganese(II), Mn^IIOMTP, produced a polymeric electron transfer salt (ETS), that has been structurally and magnetically characterized. The ETS belongs to the orthorhombic Cmca space group. The ETS has an extended one-dimensional linear chain coordination polymer motif comprised of S = 2 [Mn^IIIOMTP]⁺ and bridging S = 1/2 [TCNE]⁻˙ with an Mn–N^TCNE distance of 2.330(5) Å, and lacks solvent. The [TCNE]⁻˙ is disordered over two orientations in a 1 ∶ 1 ratio. The interchain Mn⋯Mn distance, 9.205 Å, is shorter than the intrachain distance, 9.350 Å (≡a-axis). The 2 to 300 K temperature dependence of the magnetic susceptibility can be fit to a Curie–Weiss expression with an effective θ value of +40 K. Intrachain coupling was modelled to a Seiden expression (H = −2S_a·S_b) with a J_intra of −125 K, and 10 Hz ac magnetic susceptibility indicates an ordering temperature, T_c, of 9.6 K. The frequency dependence of the ac susceptibility displays spin glass behaviour.