Coordinated H-bonding between porphyrins on metal surfaces

Using a combination of X-ray photoelectron spectroscopy (XPS) and core level shift first principles calculations, we determine the formation of an unusual intermolecular interaction between porphyrin molecules. We show that protoporphyrin IX molecules (H2PPIX) adsorbed on Cu surfaces at low temperature (LT) form molecular adlayers stabilized by a strong (1.3 eV) tetragonal coordinated H-bond. This unconventional H-bonding involves the four nitrogen atoms in the tetrapyrrole macrocycle of one molecule, four hydrogen atoms, and one of the hydroxyl oxygen atoms from the carboxylic acid groups of an adjacent molecule. The calculations demonstrate that the corresponding fingerprint of this bond is observed in both the nitrogen XPS data, showing a unique peak, and the almost unchanged 1s core level energy of the hydroxyl oxygen atoms. We explain the formation of this bond by a charge rearrangement mechanism that includes proton sharing and migration.We acknowledge funding support from the Spanish Ministerio de Ciencia e Innovación (Grant No. FIS2010-19609-C02-01, MAT2011-26534, MAT2010-21156-C03-01, and -C03-03, PIB2010US-00652), the Basque Government (IT-257-07, IT-366-07), the ETORTEK program funded by the Basque Departamento de Industria and the Diputación Foral de Guipuzcoa. R.G.M. thanks the financial support of DIPC.Peer reviewe