Effect of metal complexation on the nonlinear optical response of a conjugated ligand

Abstract

International audienceOrganic nonlinear optical materials are widely investigated materials for fabricating optoelectronic devices. Particularly organic π-conjugated systems as well as transition metal complex compounds are studied in this direction because of the strong electronic coupling between the ligand and the metal, their excellent chemical stability, and their rich photochemical and photophysical properties. In this work, comparative studies of the third-order nonlinear optical susceptibilities of a bipyridine ligand (4-(N,N-dibutylamino)-4′-(5-ethynyl-2,2′-bipyridine)-azobenzene (A) and of the corresponding heteroleptic ruthenium complex (Ru(bpy)2(La)(PF6)2 (B) (La signifies the ligand) are presented. The NLO properties were investigated by means of the Z-scan technique using a 30 ps mode-locked Nd-YVO4 laser at 532 nm with a repetition rate of 10 Hz. Our results show that the introduction of the metal in the organic complex results in a significant modification of the third-order nonlinear optical response

Unexpected High Second‐Order Nonlinear Optical Activity of Metal Complexes with Three‐Branched Hexadentate 2,2′‐Bipyridine Ligands

“…The structural motif of an electron‐donor–π‐bridge–electron‐acceptor ( d ‐π‐A) chromophore is achieved by a threefold dendritic structured compound and the addition of terminal 2,2′‐bipyridine (bpy) functions. Hexacoordinated bpy complexes appear attractive because intense metal‐ligand charge transfer transitions can affect a significant enhancement of the NLO properties . Coordination of conjugated ligands with metal atoms like Ru has resulted in a drastic enlargement of the NLO response .…”

Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

“…For the latter, transition metal complexes with -conjugated ligands are interesting for the construction of multifunctional NLO chromophores by virtue of their rich photochemical and photophysical properties, greater design flexibility, excellent chemical stability, and intense low-energy metal-to-ligand charge transfer (MLCT), as well as ligand-to-metal charge transfer (LMCT) electronic transitions [2,15]. From literature survey, the vast majority of molecules investigated for NLO effects are purely organic push-pull systems.…”

Investigation On The Crystal Structure, Third-Order Nonlinear Optical And Thermal Studies Of 4-Nitroanilinium 5-Sulfosalicylic Acid Monohydrate Single Crystal

“…The nonlinear refractive index effect may arise from different physical mechanisms such as electronic (Kerr effect) or thermal effects (focusing and defocusing). The nonlinear refractive index for the sample in this case may be attributed to thermal nonlinearity resulting from the absorption of an incident beam by the medium, which results in the deposition of heat via non-radiative decay from excited states where a transverse temperature gradient is established due to the temperature coefficient of the refractive index dn/dt [9].…”