Stable mixed-valent radicals from platinum(II) complexes of a bis(dioxolene) ligand

Three diplatinum(II) complexes [{PtL}<sub>2</sub>(μ-thea)] (H4thea=2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene) have been prepared, with diphosphine or bipyridyl “L” co-ligands. One-electron oxidation of these complexes gave radical cations containing a mixed-valent [thea ]<sup>3−</sup> ligand with discrete catecholate and semiquinonate centers separated by quaternary methylene spacers. The electronic character of these radicals is near the Robin–Day class II/III border determined by UV/Vis/NIR and EPR spectroscopies. Crystal-structure determinations and a DFT calculation imply that oxidation of the thea<sup>4−</sup> ligand may lead to an increased through-space interaction between the dioxolene π systems