High Second-Order NLO Response Exhibited by the First Example of Polymeric Film Incorporating a Diimine-Dithiolate Square-Planar Complex: The [Ni(o-phen)(bdt)]

A novel square-planar diimine dithiolate non-linear optical (NLO) chromophore, the complex [Ni(o-phen)(bdt)] (1), is reported in this paper (o-phen = dianion of 1,2-phenylendiamina; bdt = 1,2-benzenedithiolate). This compound has been fully characterized by single-crystal X-ray diffraction, UV-vis-NIR spectroscopy, cyclic voltammetry, DFT, and TD-DFT calculations. 1 crystallizes in the P-21 space group and shows an almost planar molecule. The cyclic voltammetry measurements present an irreversible anodic peak at 0.87 V and reversible and quasi-reversible reduction waves at -0.35 and -1.13 V, respectively. A medium-intense (epsilon = 1.91 x 10(4) mol(-1) dm(3) cm(-1)) absorption with a maximum at 728 nm appears in the UV-vis-NIR spectrum. The molecular second order NLO properties of 1 have been measured by the electric field induced second-harmonic generation technique in DMF solution, giving values of -1000 x 10(-48) esu for mu beta(1.907) and 356 x 10(-48) esu for mu beta(0). Furthermore, remarkable solid-state responses have been measured for polymeric films of 1. Indeed, this complex has been embedded into poly(methyl methacrylate) poled films showing high NLO response (d(33) = 1.90 +/- 0.38 pm/V), higher than those previously reported for similar push pull metal complexes. Moreover, I represents the first example of a diimine dithiolate chromophore incorporated into a NLO-active film.