Photophysics and photochemistry of iron carbene complexes for solar energy conversion and photocatalysis

Earth-abundant first row transition metal complexes are important for the development of large-scale photocatalytic and solar energy conversion applications. Coordination compounds based on iron are especially interesting, as iron is the most common transition metal element in the Earth’s crust. Unfortunately, iron-polypyridyl and related traditional iron-based complexes generally suffer from poor excited state properties, including short excited-state lifetimes, that make them unsuitable for most light-driven applications. Iron carbene complexes have emerged in the last decade as a new class of coordination compounds with significantly improved photophysical and photochemical properties, that make them attractive candidates for a range of light-driven applications. Specific aspects of the photophysics and photochemistry of these iron carbenes discussed here include long-lived excited state lifetimes of charge transfer excited states, capabilities to act as photosensitizers in solar energy conversion applications like dye-sensitized solar cells, as well as recent demonstrations of promising progress towards driving photoredox and photocatalytic processes. Complementary advances towards photofunctional systems with both Fe(II) complexes featuring metal-to-ligand charge transfer excited states, and Fe(III) complexes displaying ligand-to-metal charge transfer excited states are discussed. Finally, we outline emerging opportunities to utilize the improved photochemical properties of iron carbenes and related complexes for photovoltaic, photoelectrochemical and photocatalytic applications.