We describe preparation and magnetic properties of an organic π-conjugated polymer with very large magnetic moment and magnetic order at low temperatures. The polymer is designed with a large density of cross-links and alternating connectivity of radical modules with unequal spin quantum numbers ( S ), macrocyclic S = 2 and, cross-linking S = ½ modules, which permits large net S values for either ferromagnetic or antiferromagnetic exchange couplings between the modules. In the highly cross-linked polymer, an effective magnetic moment corresponding to an average S of about 5000 and slow reorientation of the magnetization by a small magnetic field (less than or equal to 1 oersted) below a temperature of about 10 kelvin are found. Qualitatively, this magnetic behavior is comparable to that of insulating spin glasses and blocked superparamagnets.

Stimuli-responsive multimodality imaging agents have broad potential in medical diagnostics. Herein, we report the development of a new class of branched-bottlebrush polymer dual-modality organic radical contrast agents—ORCAFluors—for combined magnetic resonance and near-infrared fluorescence imaging in vivo. These nitroxide radical-based nanostructures have longitudinal and transverse relaxation times that are on par with commonly used heavy-metal-based magnetic resonance imaging (MRI) contrast agents. Furthermore, these materials display a unique compensatory redox response: fluorescence is partially quenched by surrounding nitroxides in the native state; exposure to ascorbate or ascorbate/glutathione leads to nitroxide reduction and a concomitant 2- to 3.5-fold increase in fluorescence emission. This behaviour enables correlation of MRI contrast, fluorescence intensity and spin concentration with tissues known to possess high concentrations of ascorbate in mice. Our in vitro and in vivo results, along with our modular synthetic approach, make ORCAFluors a promising new platform for multimodality molecular imaging.