In situ formation of N-heterocyclic carbene-bound single-molecule junctions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F18%3A00492829" target="_blank" >RIV/68378271:_____/18:00492829 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jacs.8b05184" target="_blank" >http://dx.doi.org/10.1021/jacs.8b05184</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.8b05184" target="_blank" >10.1021/jacs.8b05184</a>

Jazyk výsledku

angličtina

Název v původním jazyce

In situ formation of N-heterocyclic carbene-bound single-molecule junctions

Popis výsledku v původním jazyce

Self-assembled monolayers (SAMs) formed using N-heterocyclic carbenes (NHCs) have recently emerged as thermally and chemically ultrastable alternatives to those formed from thiols. The rich chemistry and strong sigma-donating ability of NHCs offer unique prospects for applications in nanoelectronics, sensing, and electrochemistry. Although stable in SAMs, free carbenes are notoriously reactive, making their electronic characterization challenging. Here we report the first investigation of electron transport across single NHC-bound molecules using the scanning tunneling microscope-based break junction (STM-BJ) technique. We develop a series of air-stable metal NHC complexes that can be electrochemically reduced in situ to form NHC electrode contacts, enabling reliable single molecule conductance measurements of NHCs under ambient conditions. Using this approach, we show that the conductance of an NHC depends on the identity of the single metal atom to which it is coordinated in the junction. Our observations are supported by density functional theory (DFT) calculations, which also firmly establish the contributions of the NHC linker to the junction transport characteristics. Our work demonstrates a powerful method to probe electron transfer across NHC electrode interfaces, more generally, it opens the door to the exploitation of surface-bound NHCs in constructing novel, functionalized electrodes and/or nanoelectronic devices.

Název v anglickém jazyce

In situ formation of N-heterocyclic carbene-bound single-molecule junctions

Popis výsledku anglicky

Self-assembled monolayers (SAMs) formed using N-heterocyclic carbenes (NHCs) have recently emerged as thermally and chemically ultrastable alternatives to those formed from thiols. The rich chemistry and strong sigma-donating ability of NHCs offer unique prospects for applications in nanoelectronics, sensing, and electrochemistry. Although stable in SAMs, free carbenes are notoriously reactive, making their electronic characterization challenging. Here we report the first investigation of electron transport across single NHC-bound molecules using the scanning tunneling microscope-based break junction (STM-BJ) technique. We develop a series of air-stable metal NHC complexes that can be electrochemically reduced in situ to form NHC electrode contacts, enabling reliable single molecule conductance measurements of NHCs under ambient conditions. Using this approach, we show that the conductance of an NHC depends on the identity of the single metal atom to which it is coordinated in the junction. Our observations are supported by density functional theory (DFT) calculations, which also firmly establish the contributions of the NHC linker to the junction transport characteristics. Our work demonstrates a powerful method to probe electron transfer across NHC electrode interfaces, more generally, it opens the door to the exploitation of surface-bound NHCs in constructing novel, functionalized electrodes and/or nanoelectronic devices.

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

<a href="/cs/project/GA15-19672S" target="_blank" >GA15-19672S: Síly a vodivost v molekulárních kontaktech</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

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

—

Svazek periodika

140

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

8944-8949

Kód UT WoS článku

000439532000045

EID výsledku v databázi Scopus

2-s2.0-85050088888