A Mn(IV)-carbene complex with a long-lived charge transfer excited state

• Detailed photophysical investigation of a Mn(IV)-carbene complex has revealed that excitation into its lowest energy absorption band (~500 nm) results in the formation of an energetic ligand-to-metal charge transfer state with a lifetime of 16 ns, the longest reported so far for a first-row transition metal complex in room temperature solution. A so-called superoxidant, Mn(IV)-carbene exhibits an excited state potential typically only harnessed via excited states of reactive organic radical species. Furthermore, the long-lived excited state in this case is found to be a dark doublet, with its transition to the quartet ground state being spin-forbidden – a contrast to most first-row literature examples, and a possible cause of the long lifetime. Showcasing some excited state properties which even exceed those of complexes based on precious metals, these findings not only advance the library of earth abundant photosensitizers, but also shed general insight into the photophysics of d3- and related Mn-complexes.

Ämnesord

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

Nyckelord

excited state; time-resolved spectroscopy; transition-metal complex

Kemi med inriktning mot kemisk fysik

Chemistry with specialization in Chemical Physics

Publikations- och innehållstyp

vet (ämneskategori)

ovr (ämneskategori)