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Tunable interface of ruthenium porphyrins and silver

DOI: 10.1021/acs.jpcc.0c10418 DOI Help

Authors: Peter Knecht (Technical University Munich) , Paul T. P. Ryan (Diamond Light Source; Imperial College London) , David A. Duncan (Diamond Light Source) , Li Jiang (Technical University of Munich) , Joachim Reichert (echnical University of Munich) , Peter S. Deimel (Technical University of Munich) , Felix Haag (Technical University Munich) , Johannes T. Kuchle (Technical University of Munich) , Francesco Allegretti (Technical University of Munich) , Tien-Lin Lee (Diamond Light Source) , Martin Schwarz (Technical University of Munich) , Manuela Garnica (Technical University Munich) , Willi Auwärter (Technical University of Munich) , Ari Paavo Seitsonen (Université de recherche Paris-Sciences-et-Lettres, Sorbonne Université, Centre National de la Recherche Scientifique) , Johannes V. Barth (Technical University of Munich) , Anthoula C. Papageorgiou (echnical University of Munich)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: The Journal Of Physical Chemistry C

State: Published (Approved)
Published: January 2021
Diamond Proposal Number(s): 24320 , 17634

Abstract: The adsorption and monolayer self-assembly of functional metal–organic blocks on solid surfaces are critical for the physicochemical properties of these low-dimensional materials. Although modern microscopy tools are very sensitive to the lateral arrangement of such blocks, they are still unable to offer directly the complete structural analysis especially for nonplanar molecules containing different atoms. Here, we apply a combinatorial approach for the characterization of such interfaces, which enables unexpected insights. An archetypal metalloporphyrin on a catalytically active surface as a function of its molecular coverage and substituent arrangement is characterized by low-energy electron diffraction, scanning probe microscopy, X-ray photoelectron spectroscopy, normal-incidence X-ray standing waves, and density functional theory. We look into Ru tetraphenyl porphyrin (Ru-TPP) on Ag(111), which is also converted into its planarized derivates via surface-assisted cyclodehydrogenation reactions. Depending on the arrangement of the phenyl substituents, the Ru atoms have distinct electronic structures and the porphyrin macrocycles adapt differently to the surface: saddle shape (pristine Ru-TPP) or bowl shape (planarized Ru-TPP derivates). In all cases, the Ru atom resides close to the surface (2.59/2.45 Å), preferably located at hollow sites and in the interface between the plane of the porphyrin macrocycle and the Ag surface. For the more flexible pristine Ru-TPP, we identify an additional self-assembled structure, allowing the molecular density of the self-assembled monolayer to be tuned within ∼20%. This precise analysis is central to harnessing the potential of metalloporphyrin/metal interfaces in functional systems.

Journal Keywords: Surface analysis; Adsorption; Pyrroles; Molecules; Scanning tunneling microscopy

Subject Areas: Chemistry, Materials

Instruments: I09-Surface and Interface Structural Analysis

Added On: 25/01/2021 10:48

Discipline Tags:

Surfaces Physics Physical Chemistry Biochemistry Chemistry interfaces and thin films Organic Chemistry Life Sciences & Biotech

Technical Tags:

Diffraction Low Energy Electron Diffraction (LEED) X-ray Standing Wave (XSW)