Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,74-ted-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)-[(2,7-R2C(12)H(6))CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)) in the presence of piperidine. The anionic complexes Q(2)[Pt{S2C=C(C(12)H(6)R2-2,7)}(2)] [R = H, (Pr4N)(2)2a; R = t-Bu, (Pr4N)22b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl2, piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:22:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl2:pip molar ratio. The neutral complexes [Pt{S2C=C(Cl2H6R2-2,7)L-2] [L = PPh3, R = H (3a), t-Bu (3b), OMe (3c); L = PEt3, R = H (4a), t-Bu (4b), OMe (4c); L-2 = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and la-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q(2)[Pt-2{S2C=C[C12H6(t-Bu)(2)-2,7]}(4)] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt-2{S2CCH[C12H6(t-Bu)2-2.7]}(2)] (7). (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH(+) salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c center dot CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q26. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes.