The search for new charge-transfer (CT) complexes of the halogens is an attractive research area, given their importance for many practical applications such as batteries for pacemakers, drugs for wound healing and infection treatment, charge carriers in dye-sensitized solar cells (DSSCs), and supercapacitors. Thus, a variety of new CT complexes have been reported in recent years, particularly polyhalides of the lighter and more reactive halogens. Whereas halogen adducts of regular electron-pair donors such as alcohols, ethers, thioethers and thiones are quite common, stable CT complexes incorporating the extremely good thiolate donors have been described far less frequently. In fact, thiolate-dihalogen adducts (RS–→Hal2, Hal = I, Br) are instable and have never been isolated in their free form, but they can be accessed when the thiolate anion is coordinated to a metal ion. The reaction of [Ni2L(μ-OAc)][ClO4] (1) with one equiv. of dibromine in CH3CN at 0°C leds to the immediate formation of a dark brown solution, from which black lustrous crystals, chara-cterized as the paramagnetic Y2 adduct [Ni2L(μ-OAc)·Y2][ClO4] (2, 3), are obtained in 70-80 % yield (Scheme 1). Carrying out the reaction in propionitrile gave single crystals of 2·CH3CH2CN suitable for a single crystal X-ray structure analysis. The linear RS–Br–Br arrangement (S-Br-Br =178.51(3)°), the significant lengthening of the Br–Br distance to 2.6980(7) Å (as compared to 2.27 in free Br2), and a S–Br distance of 2.401(1) Å, respectively, confirm the charge-transfer nature of this complex. The S–Br distance is significantly longer than the value of ca. 2.18 Å predicted for a covalent S–Br single bond and is within the range of S–Br distances reported for bromine-thi-oether CT adducts (2.3-2.4 Å). The Ni–S(1) distances are also affected, on average these lengthen by 0.11 Å relative to 1. In the crystal structure of [Ni2L(μ-OAc)•I2]+ the RS→I–I linkages are all linear, and the I–I distances are longer than in free I2 (2.667(2) Å) in agreement with charge transfer from the thiolate to the I2. The S–I distances are also longer than the value of 2.37 Å for a covalent RS–I bond. The macrocyclic complex 1 adsorbs up to 18 molar equivalents (> 270 wt %) of iodine, although it does not exhibit permanent porosity. Infrared spectroscopic and crystallographic studies reveal that two I2 molecules are captured via thiophenolate→I2 CT interactions, which enable the reversible sorption of further I2 molecules in a polyiodide-like network. The pressure dependence of the I2 sorption indicates that [Ni2L(μ-O2CR)]ClO4 behaves like a solid ionic liquid.