Cyano-Functionalized Porphyrins on Cu(111) from One-Dimensional Wires to Two-Dimensional Molecular Frameworks: On the Role of Co-Deposited Metal Atoms

Autor(es)

dos Santos, Alisson Ceccatto ^[1] ; de Campos Ferreira, Rodrigo Cezar ^[1] ; Moreno-Lopez, Juan Carlos ^{[2, 3]} ; Barreto, Lucas ^[4] ; Lepper, Michael ^[5] ; Landers, Richard ^[1] ; Steinrueck, Hans-Peter ^[5] ; Marbach, Hubertus ^[5] ; de Siervo, Abner ^[1]

Afiliação do(s) autor(es)

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

^[2] Univ Vienna, Fac Phys, A-1090 Vienna - Austria

^[3] Yachay Tech Univ, Sch Phys Sci & Nanotechnol, Urcuqui 100119 - Ecuador

^[4] Univ Fed ABC, Ctr Ciencias Nat & Humanas, BR-09210580 Santo Andre, SP - Brazil

^[5] Friedrich Alexander Univ Erlangen Nurnberg, Lehrstuhl Phys Chem 2, D-91058 Erlangen - Germany

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRY OF MATERIALS; v. 32, n. 5, p. 2114-2122, MAR 10 2020.
• Citações Web of Science: 0

Resumo

Metal adatoms play a key role in surface diffusion, adsorption conformation, and self-assembly of porphyrin molecules on metal surfaces. Herein, we study the specific influence of coadsorption of Fe, Co, and Pd atoms on the behavior of 2H-tetiakis(p-cyano)phenylporphyrin (2H-TCNPP) on Cu(111) using scanning tunneling microscopy. Upon codeposition of Fe and Co, the molecules form one-dimensional (1D) linear chains after mild annealing on Cu(111) driven by the interaction of its cyano groups with metal adatoms. A similar behavior has been observed previously on Cu(111), mediated by Cu adatoms, where the functional CN groups were also found to lower the reaction rate of the so-called porphyrin self-metalation reaction with Cu atoms significantly, in comparison to the non-cyano-functionalized porphyrin. Upon co-deposition of Pd and mild annealing, we find a remarkably different behavior, that is, a massive reorganization from 1D molecular chains to a peculiar rectangular 2D (two-dimensional) network. The molecular appearance changes to a clover shape, which is attributed to a Pd-induced dehydrogenation and subsequent ring closure reaction of the phenyl and pyrrole groups. (AU)

• Processo FAPESP: 17/08846-7 - Determinação de parâmetros termodinâmicos na difusão e formação de nanomembranas de tetra-4-clorofenilporfirina em Cu(111)
• Beneficiário: Alisson Ceccatto dos Santos
• Linha de fomento: Bolsas no Brasil - Iniciação Científica
• Processo FAPESP: 07/54829-5 - Estrutura eletrônica e geométrica de nano materiais: um estudo por radiação sincroton
• Beneficiário: Richard Landers
• Linha de fomento: Auxílio à Pesquisa - Temático