Rigid Bay-Conjugated Perylene Bisimide Rotors: Solvent-Induced Excited-State Symmetry Breaking and Resonance-Enhanced Two-Photon Absorption.

Intramolecular charge transfer and excited-state symmetry breaking have a significant effect on the nonlinear optical properties of multipolar chromophores. Rigid and nonplanar perylene bisimide derivatives (PBIs) functionalized at bay positions were comparatively and comprehensively investigated. In apolar solvents, two quadrupolar molecular rotors showed an obvious decrease of the A 0-0 / A 0-1 ratios, suggesting strong exciton coupling with the adjacent PBI units initiated by the π-π stacking. The vanishment of the preferable dimer emission in polar solvents supported the plausible phenomena of excited-state symmetry breaking, thanks to the facile rotation around the rigid linkers. Comparative femtosecond transition absorption studies confirmed their notable differences in relaxation dynamics and the generation of radical anions (PBI •- ) and cations (PBI •+ ). The maxima two-photon absorption (2PA) wavelengths obtained for the molecular rotors were slightly red-shifted to 670 nm with intrinsic resonance-enhanced characteristics, reflecting the synergistic effect of functional positions and molecular architectures. Meanwhile, the obvious increase of significant 2PA cross-section values in polar solvents illustrated the stabilization of the symmetry-broken dipolar states. Further femtosecond Z-scan also manifested the contribution of excited-state dynamics on the nonlinear optical properties of multipolar chromophores.