Two indole-based squaraine dyes bonded to two pyrenyl groups through vinyl- and ethynyl- linkers were synthesized with the aim of enhancing the intramolecular charge transfer interaction in addition to improving their optical properties. The absorption and emission properties of these derivatives were determined in order to gain an insight into the intensity of this type of interaction, their aggregation behavior and compare them with results obtained through quantum chemical calculations. Both compounds presented high photochemical stability in THF, and the linear spectroscopic characterization revealed high extinction coefficients, large fluorescence quantum yields and relatively low tendency of forming excimers in several solvents. The nonlinear spectroscopic study revealed two-photon absorption cross section maxima greater than 10,000 GM (1 GM = 1 × 10-50 cm4 s/photon), which are improved values in comparison with the indole-based squaraine core. The experimental results were compared with time-dependent DFT calculations. These observations propose a new trend in the formulation of highly absorbing organic molecules containing pyrenyl groups for the development of new materials with Organic Light-Emitting Diode (OLED) applications. Moreover, this work contributes to the study of intramolecular charge transfer interaction and its tailoring for the improvement of the linear and nonlinear optical properties.

This dissertation contains the synthesis and characterization of squaraine based new functional materials. In the first part of this thesis work, a water soluble benzothiazolium squaraine dye was synthesized with pyridium pendents, and controlled aggregation properties were achieved. After formation of partially reversible J-aggregation on a polyelectrolyte (poly(acryl acid) sodium salt) template, the nonlinear, two-photon absorption cross section per repeat unit was found to be above 30-fold enhanced compared with nonaggregate and/or low aggregates. Using a similar strategy, sulfonate anions were introduced into the squaraine structure, and the resulting compounds exhibited good water solubilities. A ‘turn on’ fluorescence was discovered when these squaraine dyes interacted with bovine serum albumin (BSA), titration studies by BSA site selective reagents show these squaraine dyes can bind to both site I and II of BSA, with a preference of site II. Introduction of these squaraine dyes to BSA nanoparticles generated near-IR protein nano fabricates, and cell images were collected. Metal sensing properties were also studied using the sulfonates containing a benzoindolium squaraine dye, and the linear response of the absorption of the squaraine dye to the concentration of Hg2+ makes it a good heavy metal-selective sensing material that can be carried out in aqueous solution. Later, a squaraine scaffold was attached to deoxyribonucleosides by Sonogashira coupling reactions, in which the reaction conditions were modified. Iodo-deoxyuridine and bromo-deoxyadenosine were used as the deoxyribonucleosides building blocks, and the resulting squaraine dye-modified deoxyribonucleosides exhibited near-IR absorption and emission properties due to the squaraine chromophore. Interestingly, these non-natural deoxyribonucleosdies showed viscosity dependent photophysical properties, which make them nice candidates for fluorescence viscosity sensors at the cellular level. After incubation with cells, these iv viscosity sensors were readily uptaken by cell, and images were obtained showing regions of high viscosity in cells.