A Magnetically Robust Triplet Ground State Sulfur-Hydrocarbon Diradical Dication

The one- and two-electron oxidation reactions of tetrathiolated di-tert-butylpyrene compound 1 with NO[Al(ORF)4] (ORF = OC(CF3)3) resulted in radical cation salt 1•+[Al(ORF)4]− and diradical dication salt 12+••·2[Al(ORF)4]−, respectively. Both salts were isolated as stable crystals and investigated by single-crystal X-ray diffraction, EPR spectroscopy, SQUID measurements, and UV–vis spectroscopy. The electron spin density is delocalized on one single sulfur-doped ring in 1•+ and on both sulfur-doped rings in 12+••. The diradical dication 12+•• features a robust triplet ground state, representing the first example of a high-spin sulfur-hydrocarbon diradical.