TY - JOUR
T1 - Reassessing the Adsorption Behavior and on-Surface Reactivity of a Brominated Porphyrin on Cu(111)
AU - Ceccatto Dos Santos, Alisson
AU - Herrera-Reinoza, Nataly
AU - Pérez Paz, Alejandro
AU - Mowbray, Duncan John
AU - De Siervo, Abner
N1 - Funding Information:
This study was financed in part by Fundaça̅o de Amparo a Pesquisa do Estado de Sa̅o Paulo (FAPESP) (projects 2007/54829-5 and 2007/08244-5), Coordenaça̅o de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) (Finance Code 001), and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). A.C.S. and N.H.R thank CNPq for the scholarships. A.P.P. thanks UAEU for an internal start-up grant (No. 31S410). This work used the Imbabura cluster of Yachay Tech University, which was purchased under contract no. 2017-024 (SIE-UITEY-007-2017).
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/8/12
Y1 - 2021/8/12
N2 - On-surface coupling reactions and molecular conformation are essential processes for building tailored functional molecular nanostructures. Here, we study the thermal debromination and reactivity of free-base tetra(4-bromophenyl)porphyrin (H2TBrPP) on Cu(111) as a function of the substrate temperature. It has been previously reported in the literature that C-Br bonds remain intact at room temperature (RT) and that the Br···Cu(111) interaction induces a drastic surface reconstruction around the molecule periphery and a distortion in the adsorbate itself. However, based on a combination of STM and XPS experiments, supported by density functional theory (DFT) calculations, we instead demonstrate that debromination readily occurs at RT, leading to a new interpretation of both the adsorption behavior and the molecular coupling of H2TBrPP on Cu(111). For the molecules deposited on the metallic substrate held above RT, our STM measurements show the growth of ordered 2D metal-organic frameworks (MOFs).
AB - On-surface coupling reactions and molecular conformation are essential processes for building tailored functional molecular nanostructures. Here, we study the thermal debromination and reactivity of free-base tetra(4-bromophenyl)porphyrin (H2TBrPP) on Cu(111) as a function of the substrate temperature. It has been previously reported in the literature that C-Br bonds remain intact at room temperature (RT) and that the Br···Cu(111) interaction induces a drastic surface reconstruction around the molecule periphery and a distortion in the adsorbate itself. However, based on a combination of STM and XPS experiments, supported by density functional theory (DFT) calculations, we instead demonstrate that debromination readily occurs at RT, leading to a new interpretation of both the adsorption behavior and the molecular coupling of H2TBrPP on Cu(111). For the molecules deposited on the metallic substrate held above RT, our STM measurements show the growth of ordered 2D metal-organic frameworks (MOFs).
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U2 - 10.1021/acs.jpcc.1c03346
DO - 10.1021/acs.jpcc.1c03346
M3 - Article
AN - SCOPUS:85111065859
SN - 1932-7447
VL - 125
SP - 17164
EP - 17173
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 31
ER -