Reactions of [Mn{N(SiMe3)(2)}(2)](2) with 2.1 equiv of RSH, R = Ph or Mes = C6H2-2,4,6-(CH3)(3), yield compounds of the formal composition "Mn(SR)(2)". Single-crystal X-ray diffraction reveals that (1)(infinity)[Mn(SMes)(2)] forms one-dimensional chains in the crystal via mu(2)-SMes bridges, whereas (3)(infinity)[Mn-4(SPh)(8)] comprises a three-dimensional network in which adamantanoid cages composed of four Mn atoms and six mu(2)-bridging SPh ligands are connected in three dimensions by doubly bridging SPh ligands. Thermogravimetric analysis and powder diffractometry indicate an reversible uptake of solvent molecules (tetrahydrofuran) into the channels of (1)(infinity)[Mn(SMes)(2)]. Magnetic measurements reveal antiferromagnetic coupling for both compounds with J = -8.2 cm(-1) ((1)(infinity)[Mn(SMes)(2)]) and -10.0 cm(-1) ((3)(infinity)[Mn-4(SPh)(8)]), respectively. Their optical absorption and photoluminescence (PL) excitation spectra display characteristic d-d bands of Mn2+ ions in the visible spectral region. Both compounds emit bright phosphorescence at similar to 800 nm at low temperatures (<100 K). However, only (1)(infinity)[Mn(SMes)(2)] retains a moderately intense emission at ambient temperature (with a quantum yield of 1.2%). Similar PL properties are also found for the related selenolate complexes (1)(infinity)[Mn(SeR)(2)] (R = Ph, Mes).