Driving multi-step regioselectivity in on-surface polymer synthesis by molecular coverage

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F25%3A00642495" target="_blank" >RIV/68378271:_____/25:00642495 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0374494" target="_blank" >https://hdl.handle.net/11104/0374494</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/anie.202512575" target="_blank" >10.1002/anie.202512575</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Driving multi-step regioselectivity in on-surface polymer synthesis by molecular coverage

Popis výsledku v původním jazyce

On-surface synthesis has revolutionized the design of low-dimensional organic nanomaterials, introducing unprecedented families of compounds while offering precise control over their structural and functional properties. A critical challenge in this field is achieving regioselective control over covalent bond formation, which is essential for tailoring polymerization processes. Here, we demonstrate a novel approach toward regioselective polymerization on Au(111) using a dicyclopentaanthracene precursor, an acene derivative that comprise two terminal indene moieties. Through a combination of scanning tunneling microscopy, non-contact atomic force microscopy, and density functional theory calculations, we reveal a molecular coverage-dependent regioselective homocoupling mechanism. At low coverage, one-dimensional polymers formed via indenyl couplings in anti-configuration dominate, involving both five-membered rings of the precursor. Increasing the coverage to half a monolayer shifts the regioselectivity, yielding a quasi-1D staircase polymer through indenyl couplings that engage only one five-membered ring of each precursor. At higher coverages, a two-dimensional porous network emerges, driven by the activation of the four benzylic positions of the molecular precursor. Our findings highlight the ability to steer regioselectivity and, consequently, polymer dimensionality by controlling molecular coverage, significantly advancing the fields of on-surface synthesis and polymer science.

Název v anglickém jazyce

Driving multi-step regioselectivity in on-surface polymer synthesis by molecular coverage

Popis výsledku anglicky

On-surface synthesis has revolutionized the design of low-dimensional organic nanomaterials, introducing unprecedented families of compounds while offering precise control over their structural and functional properties. A critical challenge in this field is achieving regioselective control over covalent bond formation, which is essential for tailoring polymerization processes. Here, we demonstrate a novel approach toward regioselective polymerization on Au(111) using a dicyclopentaanthracene precursor, an acene derivative that comprise two terminal indene moieties. Through a combination of scanning tunneling microscopy, non-contact atomic force microscopy, and density functional theory calculations, we reveal a molecular coverage-dependent regioselective homocoupling mechanism. At low coverage, one-dimensional polymers formed via indenyl couplings in anti-configuration dominate, involving both five-membered rings of the precursor. Increasing the coverage to half a monolayer shifts the regioselectivity, yielding a quasi-1D staircase polymer through indenyl couplings that engage only one five-membered ring of each precursor. At higher coverages, a two-dimensional porous network emerges, driven by the activation of the four benzylic positions of the molecular precursor. Our findings highlight the ability to steer regioselectivity and, consequently, polymer dimensionality by controlling molecular coverage, significantly advancing the fields of on-surface synthesis and polymer science.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Angewandte Chemie - International Edition

ISSN

1433-7851

e-ISSN

1521-3773

Svazek periodika

64

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

e202512575

Kód UT WoS článku

001586775600001

EID výsledku v databázi Scopus

2-s2.0-105018491244