meso-Polyarylporphyrins are often used as components of molecules that mimic photosynthetic reaction centers by carrying out photoinduced electron-transfer reactions. Studies of these systems have raised questions concerning the role of alkyl substituents at the "beta-pyrrolic" positions on the porphyrin periphery in limiting pi-pi overlap between the macrocycle and the aryl rings. The degree of overlap affects electronic coupling and, therefore, the rates of electron-transfer reactions. There is also evidence that when the Linkages joining porphyrins to electron-acceptor or -donor moieties contain amide bonds, the sense of the amide linkage may strongly affect electron-transfer rate constants. In this study, three carotenoid-porphyrin-quinone molecular triads and various model compounds have been prepared, and electron-transfer has been studied using time-resolved emission and absorption techniques. The results show that steric hindrance due to methyl groups at the beta-pyrrolic positions reduces electron-transfer rate constants by a factor of similar to 1/5. In addition, amide-containing donor-acceptor linkages having the nitrogen atom attached to the porphyrin meso-aryl ring demonstrate electron-transfer rate constants similar to 30 times larger than those for similar linkages with the amide reversed, after correction for thermodynamic effects.