Panchromatic Absorption and Oxidation of an Iron(II) Spin Crossover Complex.

In order to expand and exploit the useful properties of d 6 -iron(II) and d 5 -iron(III) complexes in potential magnetic, photophysical, or magnetooptical applications, crucial ligand-controlled parameters are the ligand field strength in a given coordination mode and the availability of suitable metal and ligand frontier orbitals for charge-transfer processes. The push-pull ligand 2,6-diguanidylpyridine (dgpy) features low-energy π* orbitals at the pyridine site and strongly electron-donating guanidinyl donors combined with the ability to form six-membered chelate rings for optimal metal-ligand orbital overlap. The electronic ground states of the pseudo-octahedral d 6 - and d 5 -complexes mer -[Fe(dgpy) 2 ] 2+ , cis-fac -[Fe(dgpy) 2 ] 2+ , and mer -[Fe(dgpy) 2 ] 3+ as well as their charge-transfer (CT) and metal-centered (MC) excited states are probed by variable temperature UV/vis absorption, NMR, EPR, and Mössbauer spectroscopy, magnetic susceptibility measurements at variable temperature as well as quantum chemical calculations.