Two molecular materials, [3RBzTPP][Ni(mnt) 2 ] (mnt 2− =maleonitriledithiolate, [3RBzTPP] + =3-R-benzyltriphenylphosphinium, R=CN(1), F(2)), have been investigated and characterized by elemental analyses, IR, UV spectroscopy, X-ray diffraction and magnetic susceptibility measurements. The [Ni(mnt) 2 ] − anions of 1 and 2 stack into a column through the Ni⋯S or/and S⋯S interactions with a Ni⋯S distance of 3.765Å for 1 and with the Ni⋯S and S⋯S distances of 3.654Å and 3.681Å for 2. The weak CH⋯N, CH⋯F hydrogen bonds and π⋯π stacking interactions result in the forming of a 3D network structure. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 shows an antiferromagnetic coupling behavior with θ=−9.3K, and 2 exhibits a spin-gap transition with Δ/k b =945.0K around 217K.