Thermally induced intra-molecular transformation and metalation of free-base porphyrin on Au(111) surface steered by surface confinement and ad-atoms

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F20%3A00539769" target="_blank" >RIV/68378271:_____/20:00539769 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15310/20:73604248

Výsledek na webu

<a href="http://hdl.handle.net/11104/0317468" target="_blank" >http://hdl.handle.net/11104/0317468</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0na00401d" target="_blank" >10.1039/d0na00401d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermally induced intra-molecular transformation and metalation of free-base porphyrin on Au(111) surface steered by surface confinement and ad-atoms

Popis výsledku v původním jazyce

We investigated chemical transformations of a fluorinated free-base porphyrin, 5,10,15,20-tetrakis(4-fluorophenyl)-21,23H-porphyrin (2H-4FTPP) under a Au(111) surface confinement and including gold adatoms by using an experiment and density functional theory based first-principles calculations. Annealing of 2H-4FTPP led to cyclodehydrogenation of the molecule to a π-extended fused aromatic planar compound, 2H-4FPP, and metallation of the porphyrin ring by Au atoms to Au-4FPP complex. Noticeable lowering of bond-dissociation energies of the pyrrole's C–H bonds of the Au(111) supported molecule with respect to their values in the gas phase explained the observed on-surface planarization. Our findings also indicate that Au adatoms may catalyze cleavage of C–H/F bonds in temperature-initiated processes on Au surfaces. BDEs and explicit inclusion of Au adatoms helps to rationalize thermally induced chemical reactions on the respective surface.n

Název v anglickém jazyce

Thermally induced intra-molecular transformation and metalation of free-base porphyrin on Au(111) surface steered by surface confinement and ad-atoms

Popis výsledku anglicky

We investigated chemical transformations of a fluorinated free-base porphyrin, 5,10,15,20-tetrakis(4-fluorophenyl)-21,23H-porphyrin (2H-4FTPP) under a Au(111) surface confinement and including gold adatoms by using an experiment and density functional theory based first-principles calculations. Annealing of 2H-4FTPP led to cyclodehydrogenation of the molecule to a π-extended fused aromatic planar compound, 2H-4FPP, and metallation of the porphyrin ring by Au atoms to Au-4FPP complex. Noticeable lowering of bond-dissociation energies of the pyrrole's C–H bonds of the Au(111) supported molecule with respect to their values in the gas phase explained the observed on-surface planarization. Our findings also indicate that Au adatoms may catalyze cleavage of C–H/F bonds in temperature-initiated processes on Au surfaces. BDEs and explicit inclusion of Au adatoms helps to rationalize thermally induced chemical reactions on the respective surface.n

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EF16_019%2F0000754" target="_blank" >EF16_019/0000754: Nanotechnologie pro budoucnost</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

NANOSCALE ADVANCES

ISSN

2516-0230

e-ISSN

—

Svazek periodika

2

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

2986-2991

Kód UT WoS článku

000548194900040

EID výsledku v databázi Scopus

2-s2.0-85088425079