Time-resolved fluorescence and absorption techniques have been used to investigate energy and photoinduced electron transfer in a covalently linked free-base porphyrin−fullerene dyad and its zinc analog. In toluene, the porphyrin first excited singlet states decay in about 20 ps by singlet−singlet energy transfer to the fullerene. The fullerene first excited singlet state is not quenched and undergoes intersystem crossing to the triplet, which exists in equilibrium with the porphyrin triplet state. In benzonitrile, photoinduced electron transfer from the porphyrin first excited singlet state to the fullerene competes with energy transfer. The fullerene excited singlet state is also quenched by electron transfer from the porphyrin. Overall, the charge-separated state is produced with a quantum yield approaching unity. This state lives for 290 ps in the free-base dyad and 50 ps in the zinc analog. These long lifetimes suggest that such dyads may be useful as components of more complex light-harvesting systems.

Porphyrin‐C60 dyads in which the two chromophores are linked by a bicyclic bridge have been synthesized using the Diels‐Alder reaction. The porphyin singlet lifetimes of both the zinc (Pzn‐C60) and free base (P‐C60) dyads, determined by time‐resolved fluorescence measurements, are ≦17 ps in toluene. This substantial quenching is due to singlet‐singlet energy transfer to C60 The lifetime of Pzn‐1C60 is ‐5 ps in toluene, whereas the singlet lifetime of an appropriate C60 model compound is 1.2 ns. This quenching is attributed to electron transfer to yield Pznbull;+‐C60bull;‐. In toluene, P‐1C60 is unquenched; the lack of electron transfer is due to unfavorable thermodynamics. In this solvent, a transient state with an absorption maximum at 700 ran and a lifetime of‐10 μs was detected using transient absorption methods. This state was quenched by oxygen, and is assigned to the C60 triplet. In the more polar benzonitrile, P‐1C60 underoes photoinduced electron transfer to give P•+‐C60bull;‐. The electron transfer rate constant is −2 × 1011 s−1.

We have used a series of metalloporphyrin compounds to test for a relationship between the contrast of STM images and the electrochemical properties of the molecules. Molecules were tethered to a gold (111) surface by means of an isothiocyano linkage and both images and current−voltage (I−V) curves were obtained with the sample submerged in oxygen-free mesitylene. The contrast of the reducible molecules changed strongly with bias, and the corresponding I−V curves were highly asymmetric. The derivative of these curves (dI/dV) had a Gaussian-shaped peak at a voltage characteristic of the compound, although local measurements showed that there was considerable variation in this value from molecule to molecule of a given compound. These bias-dependent features were not observed in the less electroactive molecules, so the STM is capable of distinguishing electroactive molecules from non-electroactive molecules as we demonstrate with images of mixed films. We discuss one- and two-step electron-transfer mechanisms which are consistent with these observations.

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