The energetics and kinetics associated with metal porphyrin adsorption on conducting surfaces from solution are of great potential importance to the formation of self assembled structures for electronic and optical applications. In this study variable temperature solid-solution interfacial scanning tunneling microscopy (STM) imaging is used to probe the self assembly of porphyrin adlayers. We demonstrate that the adsorption of cobalt octaethylporphyrin (CoOEP) and NiOEP from phenyloctane onto Au(111) are kinetically controlled and essentially irreversible below about 100�C. Above 100�C slow desorption and re-adsorption processes allow for exchange of CoOEP and NiOEP species on the surface. Temperature and relative concentration studies provide values for the relative free energies and enthalpies of activation for the desorption process. Experimental results are compared to DFT calculated values of adsorption energy.

Temperature dependence and desorption kinetics of metal porphyrins on Au(111)

247th National Meeting (2014)

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