Competitive reversed quartet mechanisms for photogenerated ground state electron spin polarization

Photoinduced electron spin polarization (ESP) of a spin-½ organic radical (nitronyl nitroxide, NN) in a series of Pt(ii) complexes comprised of 4,4'-di-tert-butyl-2,2'-bipyridine (bpy) and 3-tert-butylcatecholate (CAT) ligands, where the CAT ligand is substituted with (CH₃)-meta-phenyl-NN (bridge-NN) groups, is presented and discussed. We show the importance of attenuating the energy gap between localized NN radical and chromophoric excited states to control both the magnitude and sign of the optically-generated ESP, and to provide deeper insight into the details of the ESP mechanism. Understanding electronic structure contributions to optically generated ESP will enhance our ability to control the nature of prepared states for a variety of quantum information science applications, where strong ESP facilitates enhanced sensitivity and readout capabilities at low applied magnetic fields and higher temperatures.