Synthesis and photophysical properties of light-harvesting arrays comprised of a porphyrin bearing multiple perylene-monoimide accessory pigments

We present the synthesis and characterization of new light-harvesting arrays containing two, four, or eight perylene-monoimide accessory pigments attached to a zinc porphyrin. Each perylene is substituted with one or three 4-tert-butylphenoxy substituents. A 4,3'- or 4,2'-diarylethyne linker joins the perylene N-imide position and the porphyrin meso-position, affording divergent or convergent architectures, respectively. The architectures are designed to provide high solubility in organic media and facile perylene-to-porphyrin energy transfer, while avoiding charge-transfer quenching of the excited porphyrin product. For the array containing four perylenes per porphyrin in both nonpolar (toluene) and polar (benzonitrile) media and for the array containing eight perylenes per porphyrin in toluene, the photoexcited perylene-monoimide dye (PMI*) decays rapidly (similar to3.5 ps) and predominantly (greater than or equal to90%) by energy transfer to the zinc porphyrin to form the excited zinc porphyrin (Zn*), which has excited-state characteristics (lifetime, fluorescence yield) comparable (within similar to10%) to those of the isolated chromophore. For the array containing eight perylenes in benzonitrile, PMI* decays similar to80% by energy transfer (forming Zn*) and similar to20% by hole transfer (forming PMI- Zn+); Zn* subsequently decays similar to20% by electron transfer (also forming PMI- Zn+) and similar to80% by the normal routes open to the porphyrin monomer (intersystem crossing, internal conversion, fluorescence). In addition to rapid and efficient perylene-to-porphyrin energy transfer, the broad blue-green to yellow absorption of the perylene dyes complements the blue absorption of the porphyrin, resulting in excellent light harvesting across a significant spectral region. Collectively, the work described herein identifies multiperylene-porphyrin arrays that exhibit suitable photochemical properties for use as motifs in larger light-harvesting systems.