Structural Analysis of Porphyrin Multilayer Films on ITO Assembled Using Copper(I)-Catalyzed Azide-Alkyne Cycloaddition by ATR IR

We report the use of grazing-angle attenuated total reflectance (GATR) IR and polarized UV-vis to determine the molecular structure of porphyrin based molecular multilayer films grown in a layer-by-layer (LbL) fashion using copper-catalyzed azide-alkyne cycloaddition (CuAAC). The molecular a orientation and bonding motif present in multilayer films of this type could impact their photophysical and electrochemical properties as well as potential applications. Multilayer films of M(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (1 M = Zn, 2 M = Cu) and azido based linkers 3-5 were used to fabricate the films on ITO substrates. Electrochemically determined coverage of films containing 2 match the trends observed in the absorbance. GATR-IR spectral analysis of the films indicate that CuAAC reactivity is leading to 1,4-triazole linked multilayers with increasing porphyrin and linker IR characteristic peaks. Films grown using all azido-linkers (3-5) display an oscillating trend in azide IR intensity suggesting that the surface bound azido group reacts with 1 and that further layering can occur through additional reaction with linkers, regenerating the azide surface. Films containing linker 5 in particular show an overall increase in azide content suggesting that only two of the three available groups react during multilayer fabrication, causing an overall buildup of azide content in the film. Films of 1 with linker 3 and 5 showed an average porphyrin plane angle of 46.4 degrees with respect to the substrate as determined by GATR FT-IR. Polarized UV-vis absorbance measurements correlate well with the growth angle calculated by IR. The orientation of the porphyrin plane within the multilayer structures suggests that the CuAAC-LbL process results in a film with a trans bonding motif.