LAUSR

A design for an octahedrally ligated phthalocyanine complex with high-spin manganese(iii) (S = 2) and MnIII(Pc)Cl2 (Pc = phthalocyanine) is presented. The presence of high-spin state MnIII in the fabricated Ph4P[MnIII(Pc)Cl2]2 (Ph4P = tetraphenylphosphonium) semiconducting molecular crystal is indicated by the Mn–Cl distance, which suggests an electronic configuration of (dyz, dzx)2(dxy)1(dz2)1. This was confirmed by the Curie constant (C = 5.69 emu K mol−1), which was found to be significantly larger than that of the isostructural Ph4P[MnIII(Pc)(CN)2]2, where MnIII adopts a low-spin state (S = 1). The magnetoresistance (MR) effects of Ph4P[MnIII(Pc)Cl2]2 at 26.5 K under 9 T static magnetic fields perpendicular and parallel to the c-axis were determined to be −30% and −20%, respectively, which are significantly larger values than those of Ph4P[MnIII(Pc)(CN)2]2. Furthermore, the negative MR effect is comparable to that of Ph4P[FeIII(Pc)(CN)2]2 (S = 1/2), which exhibits the largest negative MR effect reported for [MIII(Mc)L2]-based systems (Mc = macrocyclic ligand, L = axial ligand). This suggests that the spin state of the metal ion is the key to tuning the MR effect.