Synthesis, Linear, and Quadratic‐Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes

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Abstract
A series of D3 (FeII, RuII, ZnII, HgII) and D2d (CuI, AgI, ZnII) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 μm, and the molecular hyperpolarizability (β0) values are in the range of 200–657×10−30 esu for octahedral complexes and 70–157×10−30 esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4′‐oligophenylenevinylene‐functionalized 2,2′‐bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (λmax=482 nm, β1.91(1 e)=870×10−30 esu, β0(1 e)=657×10−30 esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers. For example, the length of the π‐conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand‐to‐metal ratio result in a substantial enhancement of β. The contribution of the metal‐to‐ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).