The impact of metalation on adsorption geometry, electronic level alignment and UV-stability of organic macrocycles on TiO2(110). Issue 25 (15th June 2017)

• Record Type: Journal Article
• Authors: Graf, Manuel; Mette, Gerson; Leuenberger, Dominik; Gurdal, Yeliz; Iannuzzi, Marcella; Zabka, Wolf-Dietrich; Schnidrig, Stephan; Probst, Benjamin; Hutter, Jürg; Alberto, Roger; Osterwalder, Jürg
• Is Part Of: Nanoscale. Volume 9:Issue 25(2017)
• Page Start: 8756
• Page End: 8763
• Publication Date: 2017-06-15
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/c7nr02317k
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : The potential sensitizer dye pyrphyrin adsorbed on TiO2 (110) is stabilized against photo-induced degradation by Co-metalation. Abstract : Metal complexes of the tetradentate bipyridine based macrocycle pyrphyrin (Pyr) have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on stoichiometric TiO2 (110) is investigated in ultrahigh vacuum by means of scanning tunneling microscopy, photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. In a joint experimental and computational effort, the local adsorption geometry at low coverage, the long-range molecular ordering at higher coverage and the electronic structure have been determined for both the bare ligand and the cobalt-metalated Pyr molecule on TiO2 . The energy level alignment of CoPyr/TiO2 supports electron injection into TiO2 upon photoexcitation of the CoPyr complex and thus renders it a potential sensitizer dye. Importantly, Co-incorporation is found to stabilize the Pyr molecule against photo-induced degradation, while the bare ligand is decomposed rapidly under continuous UV-irradiation. This interesting phenomenon is discussed in terms of additional de-excitation channels for electronically highly excited molecular states.