Supramolecular Ordering and Reactions of a Chlorophenyl Porphyrin on Ag(111)

Author(s)

de Campos Ferreira, Rodrigo Cezar ^[1] ; Paz, Alejandro Perez ^{[2, 3, 4, 5]} ; Mowbray, Duncan John ^[2] ; Roulet, Jean-Yves ^[1] ; Landers, Richard ^[1] ; de Siervo, Abner ^[1]

Affiliation

^[1] Univ Estadual Campinas, Inst Fis Gleb Wataghin, UNICAMP, BR-13083859 Campinas - Brazil

^[2] Yachay Tech Univ, Sch Phys Sci & Nanotechnol, Urcuqui 100119 - Ecuador

^[3] United Arab Emirates Univ, Coll Sci, Dept Chem & Biochem, Al Ain - U Arab Emirates

^[4] Univ Basque Country, Nanobio Spect Grp, UPV EHU, E-20018 San Sebastian - Spain

^[5] Univ Basque Country, ETSF Sci Dev Ctr, Dept Fis Mat, UPV EHU, E-20018 San Sebastian - Spain

• Document type: Journal article
• Source: Journal of Physical Chemistry C; v. 124, n. 26, p. 14220-14228, JUL 2 2020.
• Web of Science Citations: 0

Abstract

Surface-assisted Ullmann-type coupling reactions are a potential bottom-up approach for building tailored low-dimensional materials with novel physical and chemical properties. In this investigation combining scanning tunneling microscopy (STM), density functional theory (DFT), and X-ray photoelectron spectroscopy (XPS), we study the adsorption behavior, supramolecular ordering, and chemical and physical changes upon annealing of a 5,10,15,20-tetrakis(4-chlorophenyl) porphyrin (Cl4TPP) on the Ag(111) surface. At room temperature, well-ordered two-dimensional (2D) assemblies grow preferentially along the < 1 (1) over bar0 > directions, revealing the coexistence of two distinguishable porous and zigzag structures and lattice parameters. Our DFT calculations show that Cl4TPP adsorbs in the typical saddle-shape conformation on Ag(111) and that the coexistence of these two overlayers is due to translations between nearly isoenergetic adsorption sites. Furthermore, to self-polymerize the organic mesh via an on-surface Ullmann-type coupling reaction, we performed an STM and XPS study of the system upon annealing, following the chemical and structural modifications above room temperature. Under these conditions, we obtain a highly compact 2D framework composed of dechlorinated molecules. (AU)

• FAPESP's process: 17/09529-5 - Formation of 2D molecular nanopore-membranes via Ullmann reaction with tetra-4-chlorophenylporphyrin on Ag(111)
• Grantee: Jean-Yves Roulet
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 07/54829-5 - Electronic and geometric structure of nano-materials: synchrotron radiation studies
• Grantee: Richard Landers
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 07/08244-5 - Study of the magnetic properties of Pd and PdAu ultrathin films and nanoparticles by using XMCD
• Grantee: Abner de Siervo
• Support Opportunities: Regular Research Grants