Constructing Single-Chain Magnets by Supramolecular π-π Stacking and Spin Canting: A Case Study on Manganese(III) Corroles

Abstract

A single-chain magnet (SCM) was constructed from manganese(III) 5,10,15-tris(pentafluorophenyl)corrole complex [Mn(III) (tpfc)] through supramolecular π-π stacking without bridging ligands. In the crystal structures, [Mn(tpfc)] molecules crystallized from different solvents, such as methanol, ethyl acetate, and ethanol, exhibit different molecular orientations and intermolecular π-π interaction or weak Mn⋅⋅⋅O interaction to form a supramolecular one-dimensional motif or dimer. These three complexes show very different magnetic behaviors at low temperature. Methanol solvate 1 shows obvious frequency dependence of out-of-phase alternating-current magnetic susceptibility below 2 K and a magnetization hysteresis loop with a coercive field of 400 Oe at 0.5 K. It is the first example of spin-canted supramolecular single-chain magnet due to weak π-π stacking interaction. By fitting the susceptibility data χ(M) T (20-300 K) of 1 with the spin Hamiltonian expression H = -2J Σ(i=1)(n-1) S(Ai) S(Ai+1) + D Σ(i) S((iZ)(2)), the intrachain magnetic coupling parameter transmitted by π-π interaction of -0.31 cm(-1) and zero field splitting parameter D of -2.59 cm(-1) are obtained. Ethyl acetate solvate 2 behaves as an antiferromagnetic chain without ordering or slow magnetic relaxation down to 0.5 K. The magnetic susceptibility data χ(M) T (20-300 K) of 2 was fitted by assuming the spin Hamiltonian H = -2JΣ(i=1)(n-1) S(Ai) S(Ai+1), and the intrachain antiferromagnetic coupling constant of -0.07 cm(-1) is much weaker than that of 1. Ethanol solvate 3 with a dimer motif shows field-induced single-molecule magnet like behavior below 2.5 K. The exchange coupling constant J within the dimer propagated by π-π interaction is -0.14 cm(-1) by fitting the susceptibility data χ(M) T (20-300 K) with the spin Hamiltonian H = -2J S(A) S(B) + β(S((A)g(A)) + S((B)g(B)))H. The present studies open a new way to construct SCMs from anisotropic magnetic single-ion units through weak intermolecular interactions in the absence of bridging ligands.