A series of structurally-related multipolar chromophores of different symmetry (dipolar, quadrupolar, octupolar, dendritic...), and shape (rod-like, Y-shaped...) propeller-shaped, were investigated for optical power limiting based on multiphoton absorption processes. Their design is based on the functionalization of nanoscale linear or branched conjugated backbones with electro-active (i.e. electron-releasing or electron-withdrawing) peripheral and core/node groups. Their two-photon absorption (TPA) spectra were determined by investigating their two-photon-excited fluorescence properties in the NIR region using pulsed excitation in the femtosecond regime. These studies provide evidence that the charge symmetry plays an important role, the quadrupolar chromophores leading to giant TPA cross-sections in the visible red. Furthermore, modulation of the nonlinear absorptivity/transparency/photostability trade-off can be achieved by playing on the nature of the electroactive groups and of the spacers. Interestingly, higher-order charge symmetries and branched structures provide an innovative route for TPA amplification and/or spectral broadening in the NIR region.