Influence of the R-substituents on the properties of [Ni(R2pipdt)(dmit)] complexes and crystal structure where R = CH2C6H5.

[Ni(R2pipdt)(dmit)], (R2pipdt = 1,4-disubstituted-piperazine-3,2-dithione, R = CH2C6H5; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) (1b) has been prepared and characterised and the properties compared with those of the known complex 2b belonging to the same class where R = Pr i. Cyclic voltammetry of 1b and 2b was carried out and compared with that of the respective R2pipdt ligand precursors (1a and 2a ). The nature of the R-groups of the pipdt ligand exerts an effect on the redox potentials and confirmed the position of the LUMO as mainly on the R2pipdt part of the complex. Accordingly the low frequency absorption, assigned to the HOMO-LUMO transition which has inter-ligand charge-transfer character, is found for 1b at lower frequency when compared to the corresponding transition of 2b. In situ EPR was carried out on electroreduced radical species of the R2pipdt ligand precursors (1a, 2a ) and corresponding complexes (1b, 2b ). This revealed considerable delocalisation of the unpaired electron on the R2pipdt ligand in 1b and 2b with coupling constants to N and H comparable with those of 1a and 2a . Complex 1b crystallised in the space group Pnma and shows an essentially planar complex (with out-of-plane R groups) pi stacked at a distance of 3.65(1) A. Such a one-dimensional structure is not achieved in the case of 2b, where the complex units are almost parallel and head-to-tail with each other forming dimers and this difference in solid-state packing is apparent in the diffuse reflectance spectrum of each. Plane-wave DFT calculations for 1b revealed a highly one-dimensional band structure with considerable band dispersion along the direction of greatest molecular interaction via pi-stacking.