On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F23%3A73617262" target="_blank" >RIV/61989592:15640/23:73617262 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68378271:_____/23:00570914 RIV/61989592:15310/23:73617262

Výsledek na webu

<a href="https://pubs.acs.org/doi/pdf/10.1021/jacs.2c10088" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/jacs.2c10088</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.2c10088" target="_blank" >10.1021/jacs.2c10088</a>

Jazyk výsledku

angličtina

Název v původním jazyce

On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety

Popis výsledku v původním jazyce

The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square-type free-base and Zn-functionalized tetramers on Ag(100). An atomic-level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures. Complemented by density functional theory modeling, the electronic structure is elucidated, indeed revealing antiaromaticity induced by the COT moiety. The present study thus gives access, and insights, to a porphyrin oligomer, representing both a model system for directly fused porphyrins and a potential building block for conjugated, extended two-dimensional porphyrin sheets.

Název v anglickém jazyce

On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety

Popis výsledku anglicky

The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square-type free-base and Zn-functionalized tetramers on Ag(100). An atomic-level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures. Complemented by density functional theory modeling, the electronic structure is elucidated, indeed revealing antiaromaticity induced by the COT moiety. The present study thus gives access, and insights, to a porphyrin oligomer, representing both a model system for directly fused porphyrins and a potential building block for conjugated, extended two-dimensional porphyrin sheets.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2023

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

145

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

967-977

Kód UT WoS článku

000907023500001

EID výsledku v databázi Scopus

2-s2.0-85145473927