Attachment of synthetic analogs of natural tetrapyrroles to electroactive surfaces enables physicochemical interrogation and may provide material for use in catalysis, diagnostics, and energy conversion. Six synthetic zinc chlorins and one free base bacteriochlorin, tailored analogs of chlorophyll and bacteriochlorophyll, respectively, have been attached to Si(100) via a high-temperature (400°C) baking method. The hydroporphyrins bear diverse functional groups that enable surface attachment (vinyl, acetyl, triisopropylsilylethynyl, pentafluorophenyl, and hydroxymethylphenyl) and a geminal dimethyl group in each reduced ring for stabilization toward adventitious dehydrogenation. The films were examined by cyclic voltammetry, FTIR spectroscopy, X-ray photoelectron spectroscopy, and ellipsometry. Monofunctionalized and difunctionalized hydroporphyrins gave monolayer and multilayer films, respectively, indicating robustness of the hydroporphyrin molecules, but in each case the film was more heterogeneous than observed with comparable porphyrins. The data suggest that some amount of unattached molecules remain intercalated with surface-attached molecules. Additional molecular designs will need to be examined to develop a deep understanding of the structure-activity relationship for formation of homogeneous monolayers and multilayers of synthetic hydroporphyrins.
