The synthesis and excited-state dynamics are described for fixed-distance zinc diporphyrin-zinc porphyrin-pyromellitimide molecules 1-3 (D-M-Im) and zinc porphyrin-pyromellitimide molecule 7 (M-Im). The rates of charge separation (CS) and charge recombination (CR), k[sub CS] and k[sub CR], of 7 were determined in C[sub 6]H[sub 6], THF, and DMF, K[sub CS] in 7 is essentially solvent polarity independent, while k[sub CR] increases with solvent polarity. A small k[sub CR] in C[sub 6]H[sub 6] has been interpreted in terms of the small electron-transfer probability, which arises from the small solvent reorganization energy and large reaction exothermicity in the inverted region. In molecules 1-3, [sup 1](M)* is competitively quenched by D through the intramolecular singlet-singlet energy transfer to give [sup 1](D)*-M-Im and by Im through intramolecular CS to give D-(M)[sup +]-(Im)[sup [minus]]. The [sup 1](D)*-M-Im state decays to the ground state with a lifetime to that of the reference [sup 1](D)* and does not undergo any intramolecular electron-transfer reactions. On the other hand, from the initially formed ion pair (IP) state, D-(M)[sup +]-(Im), a secondary IP state, (D)[sup +]-M-(Im)[sup [minus]], is formed by hole transfer from (M)[sup +] to D in THF or DMF. Such hole transfer does not occur in less polar C[submore » 6]H[sub 6]. The lifetimes of the secondary IP states formed from 1, 2, and 3, which range from 0.25 to 23 [mu]s, depend upon both the spacer connecting the D and M and the polarity of solvent. In contrast to the case of (M)[sup +]-(Im)[sup [minus]], the lifetime of (D)[sup +]-M-(Im)[sup [minus]] increases with increasing solvent polarity. Marked differences in solvent polarity effects observed on the lifetime of the (M)[sup +]-(Im)[sup [minus]] and (D)[sup +]-M-(Im)[sup [minus]] states may have important practical implications for the design of artificial photosynthetic models. 67 refs., 9 figs., 3 tabs.« less