Structurally unique π-expanded diketopyrrolopyrroles (EDPP) were designed and synthesized. Strategic placement of a fluorene scaffold at the periphery of a diketopyrrolopyrrole through tandem Friedel-Crafts-dehydration reactions resulted in dyes with supreme solubility. The structure of the dyes was confirmed by X-ray crystallography verifying a nearly flattened arrangement of the ten fused rings. Despite the extended ring system, the dye still preserved good solubility and was further functionalized by using Pd-catalyzed coupling reactions, such as the Buchwald-Hartwig amination. Photophysical studies of these new functional dyes revealed that they possess enhanced properties when compared with expanded DPPs in terms of two-photon absorption cross-section. It is further demonstrated that in addition to the initial diacetals, the final electrophilic cyclization step can also be applied to diketones. By placing two amine groups at peripheral positions of the resulting dyes, values of two-photon absorption cross-section on the level of 2000 GM around 1000 nm were achieved, which in combination with high fluorescence quantum yield (Φfl ), generated a two-photon brightness of approximately 1600 GM. These characteristics in combination with strong red emission (665 nm) make these new π-expanded diketopyrrolopyrroles of major promise as two-photon dyes for bioimaging applications. Finally, the corresponding N-alkylated DPPs displayed a solid-state fluorescence.
Keywords: chromophores; dyes; fluorescence; heterocycles; photophysics.
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