Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled films of ruthenium phthalocyanine on organic monolayer-modified silver substrates

A self-assembled film of ruthenium phthalocyanine (RuPc) fabricated on a silver substrate pre-modified with a monolayer of 4-mercaptopyridine (PySH) or 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was studied by ultraviolet-visible (UV-Vis) and surface enhanced Raman scattering (SERS) spectroscopy. PySH or BPENB was used as a ligand to link RuPc since they not only modify the silver substrate, but also deliver a pyridyl group pointing out from the silver surface. Therefore, we can explore the relationship between the structure and orientation of metallophthalocyanine and the substrate modified by the two kinds of organic-monolayers with the different conjugates and molecular lengths. UV-Vis bands due to the organic-monolayer (PySH or BPENB) modified silver films shift to longer wavelengths and a new band arising from the metallophthlocyanine appears, suggesting the binding of RuPc to PySH/BPENB, as well as the interaction between the marcocycle of RuPc and the ring of PySH/BPENB. Vibrational bands arising from both the RuPc and PySH/BPENB moieties appear clearly in the SERS spectra of the RuPc-PySH/BPENB composite films, indicating that RuPc is successfully assembled on the top of PySH/BPENB film. The shifts and relative intensity changes of bands due to PySH or BPENB in the SERS spectra imply the binding of the metallophthalocyanine to the pyridyl group in the composite films. Furthermore, the comparison of the SERS spectra revealed that the orientations of PySH and BPENB in the two kinds of composite films are different; the BPENB moiety in the RuPc-BPENB composite film is more perpendicular to the silver surface compared with the PySH moiety in the RuPc-PySH composite film. (C) 2003 Elsevier B.V. All rights reserved.