The preparation of the novel paramagnetic nickel dithiolene complex Ni(F(2)pdt)(2)(-.) (F(2)pdt(2-): 2,2-difluoro-1,3-propanediyldithioethylene. -1,2-dithiolate) and its X-ray crystal structure as n-Bu4N+ salt are described. (nBu(4)N)[Ni(F(2)pdt)(2)] (2) crystallizes in the orthorhombic system, space group Pna2(1) with a = 21.379(4) Angstrom, b = 5.9702(18) Angstrom, and c = 18.527(4) Angstrom. The radical anions are isolated from each other by the bulky n-Bu4N+ cations and exhibit a Curie-type magnetic behavior. Two reversible redox waves corresponding to the redox couples Ni(F(2)pdt)(2)(2-/-.) and Ni(F(2)pdt)(2)(-./0) are observed at -0.55 and 0.30 V vs SCE, illustrating the electron withdrawing effect of the CF2 substituents. As a consequence, (TTF)(3)(BF4)(2) oxidation of the radical anion does not afford the neutral Ni(F(2)pdt)(2)(0) but a TTF salt formulated as [TTF](3)[Ni(F(2)pdt)(2)](3)[CH2Cl2]. It crystallizes in the triclinic system, space group P (1) over bar with a = 12.330(3) Angstrom, b = 12.726(3) Angstrom, c = 15.706(3) Angstrom, a = 91.10(3), beta = 110.78(3), and gamma = 116.01(3). Donor and acceptor moieties are organized into (TTF)(3)(2+) and [Ni(F(2)pdt)(2)](3)(2-) trimers whose dicationic and dianionic charges have been inferred from the intramolecular bond lengths evolution and the singlet-tripler magnetic behavior. These trimers arrange orthogonally to each other into chess-board-like slabs, characterized by a segregation of the CF2 fragments and further stabilized by weak C-H . . .F interactions. Extended Huckel calculations show that only the nickel dithiolene complex trimer actually contributes to the magnetic susceptibility.