Syntheses, crystal structures, and magnetic properties of two molecular materials by self-assembly of bis(maleonitriledithiolato)nickelate monoanion and substituted benzyltriphenylphosphinium

Two molecular materials, [3RBzTPP][Ni(mnt)2] (mnt2− = 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 3.765 Å for 1 and with the Ni⋯S and S⋯S distances of 3.654 Å and 3.681 Å 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 2–300 K show that 1 shows an antiferromagnetic coupling behavior with θ = −9.3 K, and 2 exhibits a spin-gap transition with Δ/kb = 945.0 K around 217 K.