Molecular Structure-Optical Property Relationship of Salicylidene Derivatives: A Study on the First-Order...

The first-order hyperpolarizability of π-conjugated organic molecules is of particular interest for the fabrication of electro-optical modulators. Thus, we investigated the relationship between the molecular structure and the incoherent second-order nonlinear optical response (β_HRS) of four salicylidene derivatives (salophen, [Zn(salophen)(OH₂)], 3,4-benzophen, [Zn(3,4-benzophen)(OH₂)]) dissolved in DMSO. For that, we employed the Hyper-Rayleigh Scattering technique with picosecond pulse trains. Our experimental results pointed out dynamic β_HRS values between 32.0 ± 4.8 × 10^-30 cm⁵/esu and 58.5 ± 8.0 × 10^-30 cm⁵/esu at 1064 nm, depending on the molecular geometry of the salicylidene molecules. More specifically, the outcomes indicate a considerable increase of β_HRS magnitude (∼30%) when in the ligands are incorporated the Zn(II) ion. We ascribed such results to the rise of the planarity of the π-conjugated backbone of the chromophores caused by the Zn(II). Furthermore, we observed an increase of ∼50% in dynamic β_HRS when there is a replacement of one hydrogen atom (salophen molecule) by an acetophenone group (3,4-benzophen). This result is related to the increase of the effective π-electron number and the higher charge transfer induced at the excited state. All these findings were interpreted and supported in the light of time-dependent density functional theory (DFT) calculations. Solvent effects were considered in the quantum chemical calculations using the integral equation formalism variant of the polarizable continuum model.