Interplay between π-Conjugation and Exchange Magnetism in One- Dimensional Porphyrinoid Polymers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F22%3A73627008" target="_blank" >RIV/61989592:15640/22:73627008 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68378271:_____/22:00561260 RIV/61388955:_____/22:00561260

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/jacs.2c02700" target="_blank" >https://pubs.acs.org/doi/10.1021/jacs.2c02700</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.2c02700" target="_blank" >10.1021/jacs.2c02700</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Interplay between π-Conjugation and Exchange Magnetism in One- Dimensional Porphyrinoid Polymers

Popis výsledku v původním jazyce

The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved . Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra-and intermolecula r oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state (S = 0) of the formed polymers, characterized by singlet-triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the pi-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

Název v anglickém jazyce

Interplay between π-Conjugation and Exchange Magnetism in One- Dimensional Porphyrinoid Polymers

Popis výsledku anglicky

The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved . Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra-and intermolecula r oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state (S = 0) of the formed polymers, characterized by singlet-triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the pi-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

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

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

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

144

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

"12725 "- 12731

Kód UT WoS článku

000829574800001

EID výsledku v databázi Scopus

2-s2.0-85134720574