Methylammonium groups at the solid walls of nanometer-sized, water-filled monolayer gaps as binding sites for a tetraanionic porphyrin

Long-chain hydrosulfides containing two secondary amide functions and eithe r electron-poor or electron-rich carbon-carbon double bonds were self-assem bled on gold surfaces around a flat-lying, octaanionic porphyrin. Rigid and reactive surface monolayers with 2 nm-wide, porphyrin-based gaps were thus obtained. The gold electrodes were then immersed in water, and the double bonds on the gaps' surfaces reacted with methylamine. It was added to the d ouble bonds either by Michael addition or by bromination with hypobromite f ollowed by methylamine substitution. Only the double bonds at the border of the gaps were accessible to methylamine dissolved in the bulk water volume and could react. The walls of the rigid membrane gaps now contained methyl ammonium groups at the sites of the double bonds in defined heights. A tetr acationic copper(II) porphyrinate could not diffuse any more into the gap a nd did not quench the fluorescence of the octaanionic porphyrin on the bott om of the gap. A tetraanionic porphyrin, on the other hand, was fixated by the ring of ammonium groups. The bound porphyrin then acted as molecular co ver for the gap with respect to ferricyanide transport from bulk water to t he electrode. It was removed by raising the pH to a value of 12, where the methylammonium groups were neutralized to amines. Lowering the pH to 7 agai n and addition of more of the anionic porphyrin reclosed the gap. The porph yrin "cover" should be localized at distances of 8-10 and 20 Angstrom from the bottom porphyrin by multiple charge interactions. The 8-10 Angstrom dis tance is ideal for studies of photoinduced electron transfer between two po rphyrin monomers of different redox potential. Furthermore it was found, th at redox-active tyrosine could be trapped in the water volume above the por phyrin on gold.