New [M(R(2)Pipdt)(2)](BF4)(2) salts [R(2)Pipdt = N,N'-dialkyl-piperazine-2,3-dithione; M = Pd(II), R = Me and M = Pt(II), R = Me, Et, Pr-i] bearing redox-active cationic dithiolene complexes have been prepared and characterized. These cations react with the redox-active [M(mnt)(2)](2-) [M = Pd(II), Pt(II); mnt = maleonitrile-2,3-dithiolate] anionic dithiolenes to form salts describable as ion pair charge-transfer complexes. X-ray crystallographic studies have shown that [M(Me(2)Pipdt)(2)][M(mnt)(2)] complexes, with M = Pd(II) and Pt(II), are isomorphous. Crystal data of the Pt salt (3a): triclinic, P (1) over bar (No. 2); Z = 1; T = 2.93(2) K; a = 6.784(7) Angstrom, b = 8.460(6) Angstrom, c = 13.510(5) Angstrom, alpha = 100.63(2)degrees, beta = 104.04(2)degrees, gamma = 96.90(2)degrees; R1 = 0.0691 [wR2 = 0.2187 (all data)]. Structural data show that approximately square-planar [Pt(Me(2)Pipdt)(2)] dications and regular square-planar [Pt(mnt)(2)] dianions form an infinite anion-cation one-dimensional stack along axis a with a Pt...Pt a/2 distance of 3.392 Angstrom and a Pt...Pt...Pt angle of 180degrees. Anions and cations arrange themselves face-to-face so as to take on a staggered arrangement. These salts exhibit strong absorptions in the visible-near-infrared region assigned to ion pair charge-transfer transitions. A relation between the optical and thermal electron transfer in the solid state is obtained using a "Marcus-Hush model", and a solid-state electrical conductivity in agreement with expectations is observed. Vibrational spectroscopy is in agreement with the existence of charge-transfer interactions between the cationic and anionic components of the salts.