Finite-temperature Fe K-edge X-ray absorption simulations reveal local structural dynamics of an iron(II) photosensitizer in solution and the crystalline phase

Abstract

Interpreting metal K-edge spectra of flexible photosensitizers requires a structural model that separates electronic signatures from thermal motion, solvent disorder, and crystal-packing effects. We combine Fe K-edge X-ray absorption measurements with second-generation Car--Parrinello ab initio molecular dynamics and all-electron Gaussian and augmented-plane-wave simulations for an iron(II) N-heterocyclic carbene photosensitizer in acetonitrile solution and in the crystalline phase. Ensemble-averaged spectra reproduce the main near-edge features in both environments and preserve the experimentally observed similarity of the first Fe coordination shell upon dissolution. Comparison with radial distributions extracted from extended fine-structure measurements validates the Fe--N and Fe--C coordination shells sampled by the trajectories, while element-resolved pair distributions explain why higher-shell experimental contrast is rapidly lost. The same dynamical ensembles reveal a broad out-of-plane distribution of the terpyridine nitrogen atom and a nearly octahedral distribution of the Fe-centered coordination planes. The results show that finite-temperature X-ray absorption simulations can provide a compact structural-dynamics picture of molecular transition metal photosensitizers by linking local spectra, solvent-phase ligand motion, and medium-range structural disorder within one trajectory-based description.