Modulation of Interfacial Electronic Coupling Between (Porphinato)metal Complexes and Gold Nanoparticles via Carbodithioate and Thiol Linkers

Tae-Hong Park and Michael J. Therien

• Porphyrin-functionalized Au nanoparticles
  • Core size: ~2 nm
  • Identical surface coverages (~37-48 ligands) manifest for both thiol and carbodithioate linkers
• 2-Au features spectroscopic characteristics not associated with 1-Au and other AuNPs which are organothiol functionalized.
• Resonance Raman data show that 2-Au porphyrin modes are dramatically enhanced relative to those for 1-Au.
• Excitation and electronic absorption spectra demonstrate that 2-Au features porphyrin-Au charge resonance interactions not present in 1-Au.

Carbodithioate linkers facilitate enhanced interfacial electronic coupling relative to the classic thiol ligand.