Tuning the LUMO energy of 1,10-phenanthroline in α-diimine–dithiolate Ni(II) complex and enhancement of nonlinear optical properties

• Chlorination increases (reduces) the π-acceptor (σ-donor) capability of 1,10-phen.
• The new complex [Ni(Cl4-phen)(mi-5edt)] has been prepared and characterized.
• NLO properties are among the highest reported so far for d8 square-planar compounds.
• Calculations confirm the role of the chlorination enhancing the NLO properties.

The synthesis, characterization, nonlinear optical properties and DFT calculations for a new Ni-diiminedithiolate complex [Ni(Cl4-phen)(mi-5edt)] (Cl4-phen = 3,4,7,8-tetrachloro-1,10-phenanthroline; mi-5edt = 1-(N-methylindol-5-yl)-ethene-1,2-dithiolate), are reported. The UV–Vis spectrum shows a solvatochromic absorption at 700 nm in DMF (ε = 5520 mol−1 dm3 cm−1) due to a charge-transfer (CT) highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) transition, typical of push–pull complexes. The CT character of this electronic transition is confirmed by DFT calculations with the HOMO mainly centered on the mi-5edt moiety and the LUMO on the Cl4-phen ligand. By comparison with the unsubstituted analogue compound, computational studies confirm the role of the chlorination enhancing the optical properties of this complex. The second order nonlinear optical properties were measured by EFISH technique (at 1.907 μm), giving values of −2030 and −810 × 10−48 esu for μβ1.907 and μβ0, respectively. These values are among the highest reported so far for the class of d8 square-planar push–pull compounds.

The chlorination effects on the orbitals’ energies of 1,10-phenanthrolines have been studied by DFT calculation on phen and two differently chlorinated analogues. On the base of these results, a new Ni-diiminedithiolate complex [Ni(Cl4-phen)(mi-5edt)] showing NLO properties, was prepared and characterized. By comparison with the unsubstituted analogue compound, computational studies confirm the role of the chlorination enhancing the optical properties of this complex.Figure optionsDownload as PowerPoint slide