Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Two photoactive iron N-heterocyclic carbene complexes [Fe-II(btz)(2) (bpy)](2+) and [Fe-III (btz)(3)](3+), where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2'-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fet(2g) levels with occupied ligand pi orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of pi-accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell Fe-III complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of Fe-III photosensitizers from those of more traditional Fe-II complexes.

Automated summary

The Resonant Photoelectron Spectroscopy (RPES) analysis of two photoactive iron N-heterocyclic carbene complexes reveals the significant impact of iron oxidation state on electronic structure, highlighting differences between Fe-III photosensitizers and traditional Fe-II complexes. The study shows strong mixing of Fet(2g) levels with occupied ligand pi orbitals but weak mixing with unoccupied ligand orbitals, emphasizing the importance of pi-accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity as a final-state effect and vibronic coupling are also observed in the complexes.