Publication Details (including relevant citation information):
Scudiero, L., Barlow, Dan E., Mazur, Ursula, Hipps, K. W. Journal of the American Chemical Society 2001 123 (17) 4073-4080
Abstract: Thin films of vapor-deposited Ni(II) and Co(II) complexes of tetraphenylporphyrin (NiTPP and CoTPP) were studied supported on gold and embedded in Al−Al2O3−MTPP−Pb tunnel diodes, where M = Ni or Co. Thin films deposited onto polycrystalline gold were analyzed by ultraviolet photoelectron spectroscopy (UPS) using He I radiation. Scanning tunneling microscopy (STM) and orbital-mediated tunneling spectroscopy (STM−OMTS) were performed on submonolayer films of CoTPP and NiTPP supported on Au(111). Inelastic electron tunneling spectroscopy (IETS) and OMTS were measured in conventional tunnel diode structures. The highest occupied π molecular orbital of the porphyrin ring was seen in both STM−OMTS and UPS at about 6.4 eV below the vacuum level. The lowest unoccupied π* molecular orbital of the porphyrin ring was observed by STM−OMTS and by IETS−OMTS to be located near 3.4 eV below the vacuum level. The OMTS spectra of CoTPP had a band near 5.2 eV (below the vacuum level) that was attributed to transient oxidation of the central Co(II) ion. That is, it is due to electron OMT via the half-filled dz2 orbital present in Co(II) of CoTPP. The NiTPP OMTS spectra show no such band, consistent with the known difficulty of oxidation of the Ni(II) ion. The STM-based OMTS allowed these two porphyrin complexes to be easily distinguished. The present work is the first report of the observation of STM−OMTS, tunnel junction OMTS, and UPS of the same compounds. Scanning tunneling microscope-based orbital-mediated tunneling provides more information than UPS or tunnel junction-based OMTS and does so with molecular-scale resolution.
Address (URL): http://dx.doi.org/10.1021/ja0100726