We report on the synthesis and third-order nonlinear optical (NLO) properties of new asymmetric (push-pull) and symmetric chromophores based on the 3.3'-bipyridine core. The nonlinear refraction as well as the linear and nonlinear absorption of these compounds has been studied. in solution, by spectroscopy and picosecond single-shot Z-scan measurements. The results are very promising, in terms of non-resonant, nonlinear refractive index in the near infrared, particularly with enhancement of the (nonlinear efficiency/transparency) trade-off afforded by the symmetrization of the chromophores. A new polymer with this structural design has also been investigated.