Spin-state dependence of the structural and vibrational properties of solvated iron(ii) polypyridyl complexes from AIMD simulations: III. [Fe(tpen)]Cl2 in acetonitrile

Abstract

In order to achieve an in-depth understanding of the role played by the solvent in the photoinduced low-spin (LS) → high-spin (HS) transition in solvated Fe(II) complexes, an accurate description of the solvated complexes in the two spin states is required. To this end, we are applying state-of-the-art ab initio molecular dynamics (AIMD) simulations to the study of the structural and vibrational properties of iron(II) polypyridyl complexes. Two aqueous LS complexes were investigated in this framework, namely, [Fe(bpy)₃]²⁺ (bpy = 2,2′-bipyridine) [Lawson Daku and Hauser, J. Phys. Chem. Lett., 2010, 1, 1830; Lawson Daku, Phys. Chem. Chem. Phys., 2018, 20, 6236] and [Fe(tpy)₂]²⁺ (tpy = 2,2′:6′,2′′-ter-pyridine) [Lawson Daku, Phys. Chem. Chem. Phys., 2019, 21, 650]. For aqueous [Fe(bpy)₃]²⁺, combining the results of forefront wide-angle X-ray scattering experiments with those of the AIMD simulations allowed the visualization of the interlaced coordination and solvation spheres of the photoinduced HS state [Khakhulin et al., Phys. Chem. Chem. Phys., 2019, 21, 9277]. In this paper, we report the extension of our AIMD studies to the spin-crossover complex [Fe(tpen)]²⁺ (tpen = N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine) in acetonitrile (ACN). The determined LS and HS solution structures of the complex are in excellent agreement with the experimental results obtained by high-resolution transient X-ray absorption spectroscopy [Zhang et al., ACS Omega, 2019, 4, 6375]. The first solvation shell of [Fe(tpen)]²⁺ consists of ACN molecules located in the grooves defined by the chelating coordination motif of the tpen ligand. Upon the LS → HS change of states, the solvation number of the complex is found to increase from ≈9.2 to ≈11.9 and an inner solvation shell is formed. This inner solvation shell originates from the occupancy by about one ACN molecule of the internal cavity which results from the arrangement of the 4 pyridine rings of the tpen ligand, and which becomes accessible to the solvent molecules in the HS state only thanks to the structural changes undergone by the complex. The presence of this inner solvation shell for the solvated HS complex probably plays a key role in the spin-state dependent reactivity of [Fe(tpen)]²⁺ in liquid solutions.