Although iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before. Here we report the Fe^III complex [Fe(ImP)₂][PF₆] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene)), showing a Janus-type dual emission from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. This behaviour is achieved by a ligand design that combines four N-heterocyclic carbenes with two cyclometalating aryl units. The low-lying π* levels of the cyclometalating units lead to energetically accessible MLCT states that cannot evolve into LMCT states. With a lifetime of 4.6 ns, the strongly reducing and oxidizing MLCT-dominated state can initiate electron transfer reactions, which could constitute a basis for future applications of iron in photoredox catalysis.

The electronic excited states of the iron(II) complex [Fe^II(tpy)(pyz-NHC)]²⁺ [tpy = 2,2′:6′,2″-terpyridine; pyz-NHC = 1,1′-bis(2,6-diisopropylphenyl)pyrazinyldiimidazolium-2,2′-diylidene] and their relaxation pathways have been theoretically investigated. To this purpose, trajectory surface-hopping simulations within a linear vibronic coupling model including a 244-dimensional potential energy surface (PES) with 20 singlet and 20 triplet coupled states have been used. The simulations show that, after excitation to the lowest-energy absorption band of predominant metal-to-ligand charge-transfer character involving the tpy ligand, almost 80% of the population undergoes intersystem crossing to the triplet manifold in about 50 fs, while the remaining 20% decays through internal conversion to the electronic ground state in about 300 fs. The population transferred to the triplet states is found to deactivate into two different regions of the PESs, one where the static dipole moment is small and shows increased metal-centered character and another with a large static dipole moment, where the electron density is transferred from the tpy to pyz-NHC ligand. Coherent oscillations of 400 fs are observed between these two sets of triplet populations, until the mixture equilibrates to a ratio of 60:40. Finally, the importance of selecting suitable normal modes is highlighted—a choice that can be far from straightforward in transition-metal complexes with hundreds of degrees of freedom.

Two closely related Fe^II complexes with 2,6-bis(1-ethyl-1H-1,2,3-triazol-4yl)pyridine and 2,6-bis(1,2,3-triazol-5-ylidene)pyridine ligands are presented to gain new insights into the photophysics of bis(tridentate) iron(II) complexes. The [Fe(N^N^N)₂]²⁺ pseudoisomer sensitizes singlet oxygen through a MC state with nanosecond lifetime after MLCT excitation, while the bis(tridentate) [Fe(C^N^C)₂]²⁺ pseudoisomer possesses a similar ³MLCT lifetime as the tris(bidentate) [Fe(C^C)₂(N^N)]²⁺ complexes with four mesoionic carbenes.

Optimal tuning meets photodynamics: the influence of various tuning strategies for range-separated density functionals on the excited-state dynamics of an iron photosensitizer and its electronic states characters are investigated.

The absorption spectra of five Fe( ii ) homoleptic and heteroleptic complexes containing strong sigma-donating N-heterocyclic carbene (NHC) and polypyridyl ligands have been theoretically characterized using a tuned range-separation functional.