The introduction of (N-2)(3-center dot) radicals into multinuclear lanthanide molecular magnets raised hysteresis temperatures by stimulating strong exchange coupling between spin centers. Radical ligands with larger donor atoms could promote more efficient magnetic coupling between lanthanides to provide superior magnetic properties. Here, we show that heavy chalcogens (S, Se, Te) are primed to fulfill these criteria. The moderately reducing Sm(II) complex, [Sm(N-dagger dagger)(2)], where N-dagger dagger is the bulky bis(triisopropylsilyl)-amide ligand, can be oxidized (i) by diphenyldichalcosenides E2Ph2 (E = S, Se, Te) to form the mononuclear series [Sm(N-dagger dagger)(2)(EPh)] (E = S, 1-S; Se, 1-Se, Te, 1-Te); (ii) S-8 or Se-8 to give dinuclear [{Sm(N-dagger dagger)(2)}(2)(mu-eta(2):eta(2)-E-2)] (E = S, 2-S-2; Se, 2-Se-2); or (iii) with Te=PEt3 to yield [{Sm(N-dagger dagger)(2)}(mu-Te)] (3). These complexes have been characterized by single crystal X-ray diffraction, multinuclear NMR, FTIR, and electronic spectroscopy; the steric bulk of N-dagger dagger dictates the formation of mononuclear complexes with chalcogenate ligands and dinuclear species with the chalcogenides. The L alpha(1) fluorescence-detected X-ray absorption spectra at the Sm L-3-edge yielded resolved pre-edge and white-line peaks for 1-S and 2-E-2, which served to calibrate our computational protocol in the successful reproduction of the spectral features. This method was employed to elucidate the ground state electronic structures for proposed oxidized and reduced variants of 2-E-2. Reactivity is ligand- based, forming species with bridging superchalcogenide (E-2)(-center dot) and subchalcogenide (E-2)(3-center dot) radical ligands. The extraordinarily large exchange couplings provided by these dichalcogenide radicals reveal their suitability as potential successors to the benchmark (N-2)(3-center dot) complexes in molecular magnets.