Spectroscopic investigation on porphyrins nano-assemblies onto gold nanorods

The interaction between gold nanorods (Au NRs), synthesized by a conventional seeded growth protocol, and the anionic tetrakis-(4-sulfonatophenyl)porphyrin (TPPS₄) has been investigated through various spectroscopic techniques. At neutral pH, the formation of H-aggregates and the inclusion of porphyrin monomers in CTAB micelles covering the nanorods have been evidenced. Under mild acidic conditions (pH=3) a nano-hybrid assembly of porphyrin J-aggregates and Au NRs has been revealed. For the sake of comparison, Cu(II) and Zn(II) metal porphyrin derivatives as well as a cationic porphyrin have been studied in the same experimental conditions, showing that: i) CuTPPS₄ forms porphyrin H-dimers onto the Au NRs; ii) ZnTPPS₄ undergoes to demetallation, followed by acidification of the central core and eventually aggregation onto Au NRs; iii) cationic porphyrin does not interact with Au NRs.