Two-photon absorption properties of multipolar triarylamino/tosylamido 1,1,4,4-tetracyanobutadienes

The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives ( 1 , 3c and 4b-c ) incorporating tosylamido and 4-triphenylamino moieties are reported. Along with those of five closely related or differently branched TCBDs derivatives ( 2 , 3a-b , 4c and 5 ), their linear and (third-order) nonlinear optical properties were investigated by electronic absorption spectroscopy and Z-scan measurements. Among these compounds, the tri-branched compounds 3c and 5 are the most active two-photon absorbers, with effective cross-sections of 275 and 350 GM at 900 nm, respectively. These properties are briefly discussed with the help of DFT calculations, focussing on structural and electronic factors, and contextualized with results obtained previously for related compounds. The structural and electronic factors influencing their two-photon absorption cross-sections of nine TCBD derivatives are discussed.