In situ formation of N-heterocyclic carbene-bound single-molecule junctions
Identifikátory výsledku
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>
Alternativní jazyky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10302 - Condensed matter physics (including formerly solid state physics, supercond.)
Návaznosti výsledku
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)
Ostatní
Rok uplatnění
2018
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
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