One-electron oxidation of the stibines Aryl Sb (1, Aryl=2,6- Pr -4-OMe-C H ; 2, Aryl=2,4,6- Pr -C H ) with AgSbF and NaBAryl (Aryl =3,5-(CF ) C H ) afforded the first structurally characterized examples of antimony-centered radical cations 1 [BAryl ] and 2 [BAryl ] . Their molecular and electronic structures were investigated by single-crystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/Vis absorption spectroscopy, in conjunction with theoretical calculations. Moreover, their reactivity was investigated. The reaction of 2 [BAryl ] and p-benzoquinone afforded a dinuclear antimony dication salt 3 [BAryl ] , which was characterized by NMR spectroscopy and X-ray diffraction analysis. The formation of the dication 3 further confirms that the isolated stibine radical cations are antimony-centered.

Four stable boron dipyrromethene (BODIPY)‐ and porphyrin‐based bis‐arylamine diradical dications were synthesized by two‐electron oxidation of their neutral molecules. The two BODIPY‐based dications have open‐shell singlet ground states. UV/Vis absorption spectra of all four dications showed large redshifts in the NIR region compared to their neutral precursors with absorption maxima at 1274 and 1068 nm for the two BODIPY‐based dications and 1746 and 2037 nm for the two porphyrin‐based dications. Thus, two new types of NIR dyes with longer wavelengths are provided by the diradical‐dication strategy, which can be applied for the generation of other NIR dyes with a range of different chromophores and auxochromes.

By using weakly coordinating anions we succeeded in the stabilization and isolation of two Würster's blue-based diradicaloid dications with saturated spacers. Their geometries and electronic structures were investigated by various experiments in conjunction with DFT calculations. Both one-dimensional alkylate-bridged dications show considerable diradical character with spacer-dependent singlet-triplet energy gaps. One of them displays a much enhanced diradical character and could basically be viewed as a pure diradical with degeneracy of singlet and triplet states. diradical, singlet, excited triplet state, Würster's blue radical cation, X-ray structure Citation:

One-electron oxidation of the stibines Aryl 3 Sb (1, Aryl = 2,6-i Pr 2 -4-OMe-C 6 H 2 ; 2, Aryl = 2,4,6-i Pr 3 -C 6 H 2 ) with AgSbF 6 and NaBAryl F 4 (Aryl F = 3,5-(CF 3 ) 2 C 6 H 3 ) afforded the first structurally characterized examples of antimony-centered radical cations 1C + [BAryl F 4 ] À and 2C + [BAryl F 4 ] À . Their molecular and electronic structures were investigated by singlecrystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/Vis absorption spectroscopy, in conjunction with theoretical calculations. Moreover, their reactivity was investigated. The reaction of 2C + [BAryl F 4 ] À and p-benzoquinone afforded a dinuclear antimony dication salt 3 2+ [BAryl F 4 ] 2 À , which was characterized by NMR spectroscopy and X-ray diffraction analysis. The formation of the dication 3 2+ further confirms that the isolated stibine radical cations are antimony-centered.

No abstract