Charge-transfer complexation and excited-state interactions in porphyrin-silver nanoparticle hybrid structures

Highly photoactive porphyrin is shown to form charge-transfer complex with silver nanoparticles. Complexation of tetra(4-aminophenyl) porphyrin (TAPP) with Ag nanoparticles is confirmed by ground-state absorption and Raman spectroscopy. Strong Raman enhancement indicates both electromagnetic and chemical enhancement. Evidence of chemical enhancement includes a selective enhancement of porphyrin Raman bands. Fast charge separation in the complex is indicated by ultrafast transient absorption and fluorescence upconversion measurements. The charge-separated state is shown to have a lifetime of 116 ± 6 ps. Porphyrin substituents are shown to play a role in the formation of charge-transfer complex.