Kinetic Stabilizationof Carbazole Nitroxides by Inclusionin a Macrocage and Their Electron Spin Resonance Characterization

Some nitroxides, for example, tetramethylpyridiniumoxide, are known as stable radicals; however, carbazole nitroxide is less stable. The kinetic stabilization of labile radicals by introduction of bulky substituents is usually effective to investigate intrinsic properties of the molecule because of small electronic perturbation induced by the substituents. In this study, macrocage molecules with a carbazole nitroxide connected by covalent bonds were newly designed as kinetically stabilized carbazole nitroxides. The nitroxides were prepared and characterized by electron spin resonance spectroscopy. The caged nitroxides presented long half-lives (∼50 h) by kinetic analysis.