Nonlinear optical properties of intriguing Ru [sigma]-acetylide complexes and the use of a photocrosslinked polymer as a springboard to obtain SHG active thin films

A. A., A. B. and C. K. gratefully acknowledge the technical support provided by Rémi Marchal.International audienceThis work reports on the design, synthesis and photo-physical properties of two ruthenium σ-alkynyl complexes. It is shown that, despite similar optical absorption features recorded in solution, the introduc- tion of a benzaldehyde moiety leads to an improved non-linear optical (NLO) response as measured by Electric Field Induced Second Harmonic (EFISH) generation and Third Harmonic Generation (THG) at 1.907 μm, both related to the second order hyperpolarizability. These structure–property relationships are rationalized based on few state modelling. Complex 2 is subsequently processed to afford composite films that demonstrate a χ2 of 1.4 pm V−1, quite remarkable given the ease of film processing implemented in this work