Homochiral Mn³⁺ Spin-Crossover Complexes: A Structural and Spectroscopic Study

Structural, magnetic, and spectroscopic data on a Mn³⁺ spin-crossover complex with Schiff base ligand 4-OMe-Sal₂323, isolated in crystal lattices with five different counteranions, are reported. Complexes of [Mn(4-OMe-Sal₂323)]X where X = ClO₄^- (1), BF₄^- (2), NO₃^- (3), Br^- (4), and I^- (5) crystallize isotypically in the chiral orthorhombic space group P2₁2₁2 with a range of spin state preferences for the [Mn(4-OMe-Sal₂323)]⁺ complex cation over the temperature range 5-300 K. Complexes 1 and 2 are high-spin, complex 4 undergoes a gradual and complete thermal spin crossover, while complexes 3 and 5 show stepped crossovers with different ratios of spin triplet and quintet forms in the intermediate temperature range. High-field electron paramagnetic resonance was used to measure the zero-field splitting parameters associated with the spin triplet and quintet states at temperatures below 10 K for complexes 4 and 2 with respective values: D₌₁ = +23.38(1) cm^-1, E₌₁ = +2.79(1) cm^-1, and D₌₂ = +6.9(3) cm^-1, with a distribution of E parameters for the S = 2 state. Solid-state circular dichroism (CD) spectra on high-spin complex 1 at room temperature reveal a 2:1 ratio of enantiomers in the chiral conglomerate, and solution CD measurements on the same sample in methanol show that it is stable toward racemization. Solid-state UV-vis absorption spectra on high-spin complex 1 and mixed S = 1/S = 2 sample 5 reveal different intensities at higher energies, in line with the different electronic composition. The statistical prevalence of homochiral crystallization of [Mn(4-OMe-Sal₂323)]⁺ in five lattices with different achiral counterions suggests that the chirality may be directed by the 4-OMe-Sal₂323 ligand.