Vibrational structure analysis of cobalt fluoro-porphyrin surface coatings on gallium phosphide

Grazing angle attenuated total reflectance Fourier transform infrared (GATR-FTIR) spectroscopy is used to characterize chemically modified gallium phosphide (GaP) surfaces containing grafted cobalt(II) porphyrins with 3-fluorophenyl substituents installed at the meso-positions. In these hybrid constructs, porphyrin surface attachment is achieved using either a two-step method involving coordination of cobalt fluoro-porphyrin metal centers to nitrogen sites on an initially applied thinfilm polypyridyl surface coating, or via a direct modification strategy using a cobalt fluoro-porphyrin precursor bearing a covalently bonded 4-vinylphenyl surface attachment group at a β-position. Both surface-attachment chemistries leverage the UV-induced immobilization of alkenes but result in distinct structural connectivities of the grafted porphyrin units and their associated vibrational spectra. In particular, the in-plane deformation vibrational frequency of metalloporphyrin components in samples prepared via coordination to the polymeric interface is characterized by an eight wavenumber shift to higher frequencies compared to that measured on metalloporphyrin-modified surfaces prepared using the one-step attachment method. The more rigid ring structure in the polymeric architecture is consistent with coordination of porphyrin cobalt centers to pyridyl-nitrogen sites on the surface graft. These results demonstrate the use of GATR-FTIR spectroscopy as a sensitive tool for characterizing porphyrinmodified surfaces with absorption signals that are close to the detection limits of many common spectroscopic techniques.