A Magnetically Robust Triplet Ground State Sulfur-Hydrocarbon Diradical Dication.

The one- and two-electron oxidation reactions of tetrathio-lated di(tert-butyl)pyrene 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 spec-troscopy, SQUID measurement and UV spectroscopy. The electron spin density is delocalized on one single sulfur-doped ring of 1•+ while on both sulfur-doped rings of 12+••. The diradical dication 12+•• features a robust triplet ground state, representing the first example of high-spin sulfur-hydrocarbon diradical.

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