First observation of capping/uncapping by a ligand of a Zn porphyrin adsorbed on Ag(100)

Abstract

A significant first step towards creation of catalytically active porphyrin-functionalised metal surfaces has been achieved.

Deprotection, Tethering, and Activation of a One-Legged Metalloporphyrin on a Chemically Active Metal Surface: NEXAFS, Synchrotron XPS, and STM Study of [SAc]P−Mn(III)Cl on Ag(100)

“…2,3,7 Supramolecular arrays are of interest with respect to the study of energy transfer and photosynthetic mechanisms 7,8 while two-dimensional porphyrin assemblies have attracted attention for possible application as chemical sensors, in molecular electronics, or as chemically switchable 2D rotors. 3,9,10 Related to this, we recently showed that a porphyrin-functionalized silver surface exhibits ligand binding and unbinding reactions characteristic of the free metalloporphyrin 11 and showed that a well-chosen ligand can strongly alter the dynamics of adsorbed porphyrins. 10 Porphyrins have been attached to oxide surfaces for use as sensors by means of organophosphonate linkers.…”

Substrate Influence for the Zn‐tetraphenyl‐porphyrin Adsorption Geometry and the Interface‐Induced Electron Transfer

“…[12][13][14][15][16][17][18][19][20][21] Most of them are scanning tunneling microscopy/spectroscopy investigations of porphyrins on metal surfaces where the macrocycle is adsorbed flat and the conformation of the meso-substituents will change as a function of the surface termination and the interaction with the substrate. [12][13][14][15][16] There are only a few studies on semiconductor surfaces [17,20] and even fewer experiments using other techniques to extract the porphyrin orientations on surfaces. [18,21] One of these experiments has shown that by changing the macrocycle porphyrin orientation from flat to almost orthogonal to the graphite surface, the function of the system changes as well.…”

Deprotection, Tethering, and Activation of a Catalytically Active Metalloporphyrin to a Chemically Active Metal Surface: [SAc]4P−Mn(III)Cl on Ag(100)

“…We have previously made a porphyrin-functionalized silver surface that exhibits ligand binding, unbinding and displacement reactions characteristic of the free metalloporphyrin 11 and have also used well-chosen ligands to dramatically alter their dynamics. 12 Such weakly bound systems are unlikely to be sufficiently robust for catalytic applications, however, especially in the presence of a solvent where resistance to leaching is an essential attribute.…”