Nonlinear optical properties of a new panchromatic series of water-soluble bicationic push-pull fluorophores

Six water-soluble bications, characterized by a symmetric A+-pi-D-pi-A+ structure, were synthesized and comprehensively studied for their absorption and fluorescence properties, and their nonlinear optical response. Generally, the photobehavior exhibited by the six systems was found to be dependent on the molecular dimensionality and conjugation, unveiling the role of different electron-donor (dimethoxy-phenylene vs bithiophene) and electron-acceptor (methyl-pyridinium, methyl-quinolinum, and pyrimidin-pyridinium) substituents bound in different positions (ortho/para). Steady-state measurements revealed this series as a panchromatic family of dyes with noticeable absorption and emission abilities, covering the entire visible spectrum - from the near-ultraviolet to the near-infrared spectral region. Femtosecond-resolved spectroscopy disclosed the presence of ultrafast intramolecular charge transfer processes, as also predicted by TD-DFT calculations, from the central electron-rich moiety of the molecule towards the two lateral positively charged units. Further and for the first time, a solvatochromic method was successfully applied to this kind of quadrupolar double-charged compounds in order to estimate their static and dynamic second-order hyperpolarizability coefficients. Thanks to their appreciable fluorescence capability, significant Two-Photon Absorption cross-sections were also measured for all six dyes by means of the Two-Photon Excited Fluorescence technique. These findings, together with their good water solubility, designate these eye-catching fluorophores as potential candidates for bioimaging applications.

Automated summary

Six water-soluble bications with a symmetric A+-pi-D-pi-A+ structure were synthesized and studied for their absorption, fluorescence properties, and nonlinear optical response. The molecules exhibited a panchromatic family of dyes covering the entire visible spectrum and displayed ultrafast intramolecular charge transfer processes. These compounds, with significant fluorescence capability and good water solubility, show potential for bioimaging applications.