A series of zinc(II) complexes (1-6) with the ligands 4 0 ,5 0 -diaza-9 0 -(4,5-bis(methylthio)-1,3-dithiol-2ylidene) fluorene (L 1 ) or 4 0 ,5 0 -diaza-9 0 -(4,5-bis(ethylthio)-1,3-dithiol-2-ylidene) fluorene (L 2 ) have been prepared in the presence of different zinc(II) salts, 5), and [Zn(L 2 ) 2 (ClO 4 ) 2 ] (6). Five of the complexes (1-3, 5, and 6) have been structurally characterized by single-crystal X-ray diffraction. The preferred coordination geometry of the zinc(II) center is related to the coordinated anions. Complexes 1, 2 and 6 with oxo-anions display distorted octahedral geometry, while complexes 3 and 5 with chloride anions take five-and four-coordination geometries. The weak coordinated perchlorate anion prefers a trans structure, while the strong coordinated nitrate anion favors a cis structure. The intermolecular C/C, C/S, and S/S interactions lead to the assembly of the complexes into different supramolecular frameworks. The results of the 1 H NMR, UV-vis, and fluorescent spectra display a large effect of metal coordination on the electron density of the ligand. Spectral data for the complexes is in agreement with the crystal structures. Finally, semi-empirical PM3 calculations were carried out to explain the relationship of the structures and the spectra.