The electroactivity of metal–organic frameworks (MOF), hybrid materials composed of inorganic vertices connected to organic linkers, have recently been investigated, despite the intrinsic insulating nature of carboxylate bonds utilized to form MOFs. To date, only a few reports have existed on charge transport with a few using redox active metalloporphyrin cobalt-based porphyrin MOF films. Porphyrins are advantageous, because their large extinction coefficients and distinct spectra sensitive to varying oxidation state make them ideal platforms for spectroelectrochemical studies. For solar energy conversion schemes, it is practical to prepare the MOF as a thin film [1-4]. One way to do this is by layer by layer (LBL) growth. This allows for direct attachment to the electrode surface, control of film thickness, and unobstructed access to pore cavities and available active sites. In this study, our MOF-like films are composed of three components—zinc, tetracarboxylate zinc porphyrin (ZnTCPP), and a pillar (1,4-diazabicyclodiooctane, bipyridyl, or tetraazine). We find that the fabrication of films by LBL is not only reproducible with films exhibiting similar UV-Vis spectra and cyclic voltammograms, but that hopping rates are not drastically different as a function of pillar length. Future work will involve measuring hopping rates for sheets of porphyrin after different chemical treatments and in different electrolyte concentrations and types.<br/><br/>

Preliminary electrochemical studies on effects of linker length and metal nodes on redox hopping in layer-by-layer assembled metalloporphyrin metal-organic framework-like thin films

253rd National Meeting (2017)

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