Self-metalation of a free-base porphyrin on a metal oxide surface mediated by extended defects: Insight from ab initio molecular dynamics simulations

Malcıoğlu, Osman Barış
Bockstedte, Michel
An important pathway for functionalization of porphyrin-based organic-inorganic structures is the metalation of porphyrins. Recently, the porphyrin metalation was demonstrated on different metal oxide surfaces, however, the underlying mechanisms regarding the role of the surface morphology, the substituted metal, and ligands are still under investigation. Here we address the adsorption and self-metalation of H2TPP on a MgO(001) surface with low-coordinated sites. We employ ab initio molecular dynamics simulations around room temperature to provide insight into dynamic steric effects. We observe that H2TPP is mobile on the pristine surface as the steric hindrance by phenyl rings prevents the physisorption of the macrocycle at a specific site. In contrast, step edges or kink sites provide anchor points exposing low-coordinated, reactive oxygen-sites to hydrogens of the macrocycle. We report a spontaneous proton transfer at these sites forming an intermediate complex before the metalation occurs. The energetics of the self-metalation reaction is modeled.
Surface Science


Interaction of nitrite with alkali oxides
Erkoc, F; Erkoc, F (2002-07-05)
The structural and electronic properties of nitrite (ONO) and alkali oxides (OX; X = H, Li, Na, K) have been investigated theoretically by performing ab initio calculations in the HF level. These species form alkali-metal nitrates (ONOOX). The optimized structures and the electronic properties of the systems ONO, OX, and ONOOX are obtained.
Theory of impurity induced lattice distortions in the normal phase of charge density wave systems
Turgut, Sadi (1994-05-01)
A phenomenological Ginzburg-Laundau theory is applied to the normal phase of one-dimensional charge-density-wave systems with a finite concentration of impurities. It is found that the interaction between the impurities and the highly polarizable electron gas leads to a strong and oscillatory impurityimpurity interaction, which in turn leads to ordered impurity arrangements and to sizeable periodic lattice distortions. The effect is very strongly dependent on the charge of the impurities, their concentratio...
Multinucleon transfer in central collisions of U-238+U-238
Ayik, S.; YILMAZ, BÜLENT; YILMAZ TÜZÜN, ÖZGÜL; Umar, A. S.; Turan, Gürsevil (2017-08-14)
Quantal diffusion mechanism of nucleon exchange is studied in the central collisions of U-238 + U-238 in the framework of the stochastic mean-field (SMF) approach. For bombarding energies considered in this work, the dinuclear structure is maintained during the collision. Hence, it is possible to describe nucleon exchange as a diffusion process for mass and charge asymmetry. Quantal neutron and proton diffusion coefficients, including memory effects, are extracted from the SMF approach and the primary fragm...
Peptide stapling by late-stage Suzuki-Miyaura cross-coupling
Gruss, Hendrik; Feiner, Rebecca C.; Mseya, Ridhiwan; Schroeder, David C.; Jewginski, Michat; Mueller, Kristian M.; Latajka, Rafat; Marıon, Antoıne; Sewald, Norbert (2022-01-01)
The development of peptide stapling techniques to stabilise alpha-helical secondary structure motifs of peptides led to the design of modulators of protein-protein interactions, which had been considered undruggable for a long time. We disclose a novel approach towards peptide stapling utilising macrocyclisation by late-stage Suzuki-Miyaura cross-coupling of bromotryptophan-containing peptides of the catenin-binding domain of axin. Optimisation of the linker length in order to find a compromise between both...
On symplectic quotients of K3 surfaces
Cinkir, Z; Onsiper, H (Elsevier BV, 2000-12-18)
In this note, we construct generalized Shioda-Inose structures on K3 surfaces using cyclic covers and almost functoriality of Shioda-Inose structures with respect to normal subgroups of a given group of symplectic automorphisms.
Citation Formats
O. B. Malcıoğlu and M. Bockstedte, “Self-metalation of a free-base porphyrin on a metal oxide surface mediated by extended defects: Insight from ab initio molecular dynamics simulations,” Surface Science, vol. 723, pp. 0–0, 2022, Accessed: 00, 2023. [Online]. Available: