Exploration of New Stable Neutral Radicals Based on Phenalenyl

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Design and synthesis of new stable open-shell molecular systems can contribute the development not only for fundamental spin chemistry but also for exploration of spin-mediated new molecular functionalities. Recently, we succeeded in the stabilization and isolation of the new derivative of phenalenyl which is an odd-alternant hydrocarbon with high symmetry, D3h, by introducing tert-butyl groups at three β positions. In this scientific research, we have further designed new stable neutral radicals based on the phenalenyl with tert-butyl groups as stabilization substituents and synthesized new neutral radicals as follows: 1)2, 5, 8-tri-t-butyl-l, 3-diazaphenalenyl which possesses isoelectronic spin structure with phanalenyl and show the heteroatom effect on spin distribution and thermochromism, 2)2, 5-di-t-butyl-6-oxophenalenoxyl derivatives which show a remarkable change in topological symmetry of the π-electron via heteroatomic perturbation such as the delocalization nature of the introduced oxygen atoms, 3)2, 5, 8-tri-t-butyl-4-oxophenalenoxyl whose π-conjugation network in phenalenyl radical is extended to control the spin density distribution topologically, 4)2, 5-di-t-butyl-6-oxophenalenoxyl derivatives which demonstrate the crystal engineering in magnetic interactions phenalenyl-based spin-delocalized neutral π-radicals by electronic and steric effects.