Cryo IR Spectroscopy of [Hemin]⁺ Complexes in Isolation

We present cryo IR spectra of isolated [Hemin]⁺ adducts with CO, N₂, and O₂ ([Hemin(CO)₁]⁺, [Hemin(CO)₂]⁺, [Hemin(¹⁴N₂)]⁺, [Hemin(¹⁵N₂)]⁺, and [Hemin(O₂)]⁺). Well resolved bands allow for the elucidation of structure and spin multiplicity in conjunction with density functional (DFT) calculations. There is a quartet spin state for the N₂ and CO adducts and a sextet spin state for the O₂ adduct, where the O₂ retains its triplet state. The double CO adsorption induces significant changes in the vibrational patterns of the IR spectra, which we take as strong evidence for a spin quenching into a doublet. Our study characterizes [Hemin]⁺, which is the Fe³⁺ oxidation product of heme that is of ubiquitous presence in hemeproteins.