Influence of Coordinated Triflate Anions on the Solution Magnetic Properties of a Neutral Iron(II) Complex

In an effort to probe the impacts of speciation on spin-state switching, the synthesis and unique solution-phase magnetic properties of [((^TIPSC≡C)₃tren)Fe(OTf)₂] (1) are described. Analysis of the single-crystal X-ray diffraction data shows that the tris(iminoalkyne) ligand coordinates to the iron(II) center through all four nitrogen atoms, while the other two coordination sites are filled by the oxygen atoms from triflate anions. Solid-state variable-temperature (VT) magnetic studies show that 1 remains high-spin (HS) at all temperatures. In the presence of moderately strong coordinating solvents, solvent replaces the two bound triflate counteranions, as observed by ¹⁹F NMR spectroscopy and supported by conductivity measurements. VT solution measurements show 1 to be in the HS state when this solvent is oxygen-donating but low-spin (LS) with a nitrogen-donating solvent. In the noncoordinating solvent dichloromethane, both triflates are bound to the iron(II) center at room temperature, but upon cooling, 1 undergoes a coordination change, resulting in the loss of one triflate, as shown by ¹⁹F NMR. With the moderately coordinating solvent acetone, triflate dissociation upon cooling results in a spin-switching species with a T_1/2 value of 171 K, characterized via ¹⁹F NMR, Evans' method, and solution magnetometry measurements. Solution magnetic measurements collected in structurally similar cyclopentanone suggest that the spin-state switching event is exclusive to the acetone environment, suggesting the influence of both the local coordination environment and aggregation. Additionally, a comparison of the solvodoynamic diameters via dynamic light scattering suggests that aggregation of 1 is significantly different in (CH₃)₂CO and (CD₃)₂CO, leading to the observation of spin-switching behavior in the former and fully HS behavior in the latter. This study highlights the sensitivity of solution magnetic properties to solvent choice.