Synthesis and Photophysical Investigation of New Porphyrin Derivatives with β-Pyrrole Ethynyl Linkage and Corresponding Dyad with [60] Fullerene

Two new β-substituted arylethynyl <i>meso</i>-tetraphenylporphyrins, 2-[(4‘-formyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system A) and 2-[(4‘-methyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system B) and their zinc derivatives were synthesized by palladium catalysis, using a synthetic approach that affords high yields of the target systems. Comparative ultraviolet−visible (UV−vis), NMR, and cyclic voltammetry studies of such macrocycles reveal the presence of an extensive conjugation between the tetrapyrrolic ring and the linker, through π−π orbital interaction. This interaction was observed in the form of a “push−pull” effect that moves the electronic charge between the porphyrin and the aldehyde group of system A. System B, bearing a methyl group instead of the formyl group, was synthesized in order to evaluate the effect of the substitution on the charge delocalization, which is necessary to corroborate the push−pull mechanism hypothesis. The new porphyrin, system A, was also used as a starting material for the synthesis of new porphyrin−fullerene dyads in which the [60]fullerene is directly linked to the tetrapyrrolic rings by ethynylenephenylene subunits. Fluorescence and transient absorption measurements of the new dyads reveal that ultrafast energy and electron transfer occur, respectively, in nonpolar and polar solvents, with high values of the rate constant. The UV−vis, NMR, and cyclic voltammetry results show that it is possible for both energy and electron transfer between porphyrin and fullerene to take place through the π-bond interaction. Such results evidence that the coupling between the donor and acceptor moieties is strong enough for possible photovoltaic applications.