Photoelectron Imaging Study of the Diplatinum Iodide Dianions [Pt(2)I(6)](2–) and [Pt(2)I(8)](2–)

[Image: see text] Photoelectron spectroscopy has been used to study the electronic structure, photodetachment, and photodissociation of the stable diplatinum iodide dianions [Pt(2)I(6)](2–) and [Pt(2)I(8)](2–). Photoelectron spectra over a range of photon energies show the characteristic absence of low kinetic energy photoelectrons expected for dianions as a result of the repulsive Coulomb barrier (RCB). Vertical detachment energies of ∼1.6 and ∼1.9 eV and minimum RCBs of ∼1.2 and ∼1.3 eV are reported for [Pt(2)I(6)](2–) and [Pt(2)I(8)](2–), respectively. Both of the diplatinum halides exhibit three direct detachment channels with distinct anisotropies, analogous to the previously reported spectra for PtI(2)(–) and PtI(–), suggesting a platinum-centered molecular core that dominates the photodetachment. Additionally, evidence for two-photon photodissociation and subsequent photodetachment channels producing I(–) are observed for both dianions. Finally, an unexplained feature is observed at photon energies around 3 eV, whose origin is considered. Our work highlights the complex electronic structure of the heavy platinum-halide dianions that are characterized by a dense manifold of electronic states.