A new concept of charge stabilization via delocalization of the pi-cation radical species over the donor macrocycle substituents in a relatively simple donor-acceptor bearing multimodular conjugates is reported. The newly synthesized multimodular systems were composed of three covalently linked triphenylamine entities at the meso position of the porphyrin ring and one fulleropyrrolidine at the fourth meso position. The triphenylamine entities were expected to act as energy transferring antenna units and to enhance the electron donating ability of both free-base and zinc(II) porphyrin derivatives of these pentads. Appreciable electronic interactions between the meso-substituted triphenylamine entities and the porphyrin pi-system were observed, and as a consequence, these moieties acted together as an electron-donor while the fullerene moiety acted as an electron-acceptor in the multimodular conjugates. In agreement with the spectral and electrochemical results, the computational studies performed by the DFT B3LYP/3-21G(*) method revealed delocalization of the frontier highest occupied molecular orbital (HOMO) over the triphenylamine entities in addition to the porphyrin macrocycle. Free-energy calculations suggested that the light-induced processes from the singlet excited state of porphyrins are exothermic in the investigated multimodular conjugates. The occurrence of photoinduced charge-separation and charge-recombination processes was confirmed by the combination of time-resolved fluorescence and nanosecond transient absorption spectral measurements. Charge-separated states, on the order of a few microseconds, were observed as a result of the delocalization of the pi-cation radical species over the porphyrin macrocycle and the meso-substituted triphenylamine entities. The present study successfully demonstrates a novel approach of charge-stabilization in donor-acceptor multimodular conjugates.

Using a diacetylamidopyridine/uracil complementary hydrogen-bonding motif, a novel bis(zinc porphyrin)fullerene supramolecular triad is constructed and characterized. The geometry of the triad deduced from DFT-MO studies revealed the presence of the "three-point" hydrogen bonding and that one of the porphyrin units of the dimer is closer to the fullerene entity. Picosecond time-resolved emission and nanosecond transient absorption techniques were employed, respectively, to evaluate the kinetics of electron transfer and to characterize the electron-transfer products. The positioning of the porphyrin entity with respect to the fullerene entity (near or far) seems to influence the kinetics of charge-separation and charge-recombination events, thus delineating the structural importance of the studied supramolecular triad in governing the electrontransfer rates.

Photoinduced energy transfer and electron transfer processes have been found between the excited singlet state of Zn-porphyrin and C(60) via an oligothienylenevinylene bridge depending on the length of the oligothiophene and solvent polarity.