Thiolate-Bound Thulium Compounds: Synthesis, Structure, and NIR Emission

Molecular (DME)2Tm(SC6F5)3 and tetrametallic (DME)4(μ2-SPh)8Tm4(SPh)4 have been isolated in high yield and characterized by conventional methods. The fluorinated thiolate has an eight-coordinate Tm(III) ion bound to three sulfur atoms from the thiolates, four oxygen donors from the THF ligands, and a relatively weak dative Tm-F interaction with a 2.842(3)Å Tm-F separation. The benzenethiolate compound crystallizes as a tetramer with an alternating number (3, 2, 3) of thiolates connecting the nearly linear array of Tm(III) ions. Emission properties of both thiolates and the chalcogen-rich cluster (THF)6Tm4Se9(SC6F5)2 have been established. The Ph compound is significantly more emissive than either of the fluorinated species.