Decoupling chemically active 2D molecular overlayers from the substrate: chlorophenyl porphyrins on graphene/Ir(111)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F23%3A00583161" target="_blank" >RIV/68378271:_____/23:00583161 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0351153" target="_blank" >https://hdl.handle.net/11104/0351153</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcc.3c00235" target="_blank" >10.1021/acs.jpcc.3c00235</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Decoupling chemically active 2D molecular overlayers from the substrate: chlorophenyl porphyrins on graphene/Ir(111)

Popis výsledku v původním jazyce

The synthesis of atomically precise chemically active 2D molecular overlayers may be hindered by chemical interactions with the underlying substrate, especially when based on chlorophenyl porphyrins. At the same time, the chlorination of graphene, i.e., the covalent bonding of chlorine atoms with sp2 carbon atoms, is known to have a significant influence on the electronic properties of pristine graphene. In this study, we deposit a chlorinated porphyrin molecule, namely 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (Cl4TPP), on graphene/Ir(111). Employing a combined experimental and theoretical approach, we demonstrate that the porphyrin layer physisorbed on graphene self-assembles into a periodic square-like arrangement. This carpet-like growth is unperturbed by the step edges of the substrate, neither in its periodicity nor in its orientation. In addition, the molecular overlayer is thermally stable and does not alter the electronic properties of graphene. Remarkably, we show that Cl4TPP does not experience a dechlorination reaction with the underlying substrate, even after postdeposition annealing temperatures as high as 550 K. Moreover, postdeposition annealing at 700 K suggests the Cl4TPP molecules desorb intact without affecting graphene’s electronic properties. In so doing, we demonstrate the effectiveness of graphene physisorbed on Ir(111) to both promote the formation and preserve the properties of chemically reactive 2D overlayers based on chlorophenyl porphyrins. These results show physisorbed graphene’s potential as a general templating material for the formation of highly reactive self-assembled 2D overlayers.

Název v anglickém jazyce

Decoupling chemically active 2D molecular overlayers from the substrate: chlorophenyl porphyrins on graphene/Ir(111)

Popis výsledku anglicky

The synthesis of atomically precise chemically active 2D molecular overlayers may be hindered by chemical interactions with the underlying substrate, especially when based on chlorophenyl porphyrins. At the same time, the chlorination of graphene, i.e., the covalent bonding of chlorine atoms with sp2 carbon atoms, is known to have a significant influence on the electronic properties of pristine graphene. In this study, we deposit a chlorinated porphyrin molecule, namely 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (Cl4TPP), on graphene/Ir(111). Employing a combined experimental and theoretical approach, we demonstrate that the porphyrin layer physisorbed on graphene self-assembles into a periodic square-like arrangement. This carpet-like growth is unperturbed by the step edges of the substrate, neither in its periodicity nor in its orientation. In addition, the molecular overlayer is thermally stable and does not alter the electronic properties of graphene. Remarkably, we show that Cl4TPP does not experience a dechlorination reaction with the underlying substrate, even after postdeposition annealing temperatures as high as 550 K. Moreover, postdeposition annealing at 700 K suggests the Cl4TPP molecules desorb intact without affecting graphene’s electronic properties. In so doing, we demonstrate the effectiveness of graphene physisorbed on Ir(111) to both promote the formation and preserve the properties of chemically reactive 2D overlayers based on chlorophenyl porphyrins. These results show physisorbed graphene’s potential as a general templating material for the formation of highly reactive self-assembled 2D overlayers.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

1932-7455

Svazek periodika

127

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

8751-8758

Kód UT WoS článku

000984954800001

EID výsledku v databázi Scopus

2-s2.0-85156275533