Synthesis, Crystal Structures, and Nonlinear Optical (NLO) Properties of New Schiff-Base Nickel(II) Complexes. Toward a New Type of Molecular Switch?

An H2L Schiff-base ligand that was obtained from the monocondensation of diaminomaleonitrile and 4-(diethylamino)salicylaldehyde is reported together with four related nickel(II) complexes formulated as [Ni(L)(L‘)] (L‘ = MePhCHNH2,
iPrNH2, Py, and PPh3). Crystal structures have been solved for H2L, [Ni(L)(MePhCHNH2)], and [Ni(L)(iPrNH2)].
Surprisingly, the complexation process leads to the formation of a rather unusual nickel amido (−NH−NiII) bond by
deprotonation of the primary amine of H2L. A reduction of the quadratic hyperpolarizability (β) from 38 × 10-30 to
17.5 × 10-30 cm5 esu-1 is evidenced on H2L upon metal complexation by the electric-field-induced second-harmonic
(EFISH) technique. Qualitative ZINDO/SCI quantum chemical calculations indicate that, in [Ni(L)(MePhCHNH2)],
the β orientation strongly depends on the laser wavelength. In particular, a β rotation strictly equal to 90° could
be obtained with 1.022 μm incident light on passing from [Ni(L)(MePhCHNH2] to a hypothetical [Ni(HL)(MePhCHNH2]+
protonated complex, thus raising the possibility for a new type of molecular switch.