Octupolar trisporphyrin conjugates exhibiting strong two-photon absorption

We report octupolar trisporphyrin conjugates, derived from the symmetrical functionalization of a triphenylamine core with three ethynylporphyrin wings, exhibiting largely enhanced two-photon absorption (TPA) compared to the porphyrin monomers. Octupolar trisporphyrin conjugate tris-H2P was synthesized by the Pd(0)-catalyzed Sonogashira cross-coupling reaction of tris(4-iodophenyl)amine with 5,10,15-tri-(p-tolyl)-20-ethynylporphyrin, and fully characterized by various spectroscopic methods and elemental analysis. The optimized geometry of tris-H2P obtained by semi-empirical AM1 calculations reveals that tris-H2P adopts a propeller-shaped structure. Our photophysical studies strongly manifest that the trisporphyrin conjugates are promising octupolar fluorophores with effective pi-conjugation over the porphyrin wings through the octupolar core. The trisporphyrin conjugates exhibit much larger TPA cross-section values in comparison with the monomers; the TPA cross-section sigma((2)) value of tris-ZnP (11,800 GM) exceeds that of mono-ZnP (630 GM) by about 20 times. (C) 2008 Elsevier Ltd. All rights reserved.