Evidence for efficient anchoring in nitroxyl radical thin films: an experimental XPS/NEXAFS and theoretical DFT/TD-DFT study
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F24%3A10484662" target="_blank" >RIV/00216208:11320/24:10484662 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=iRUk2Qjfo7" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=iRUk2Qjfo7</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d4tc00427b" target="_blank" >10.1039/d4tc00427b</a>
Alternative languages
Result language
angličtina
Original language name
Evidence for efficient anchoring in nitroxyl radical thin films: an experimental XPS/NEXAFS and theoretical DFT/TD-DFT study
Original language description
Studies of persistent organic radical films on conductive metal surfaces can pave the way for diverse applications such as improved spin probes and labels, data control and storage, spintronics, and quantum computing. We grew monolayer films of three nitroxyl radicals (NRs), viz. TEMPO and two carbamoyl-proxyl radicals (nit8 and nit9) under ultra-high vacuum conditions on Au(111) and Cu(111) surfaces. The electronic properties of the films and NR adsorption mechanisms were analyzed by means of X-ray photoelectron (XPS) and absorption (NEXAFS) spectroscopies, with the aid of density functional theory (DFT) and time-dependent DFT computations performed on large unit cells (rev-PBE) and clusters (CAM-B3LYP). We found that all three NRs physisorb weakly on Au. In the case of nit8 and nit9, H-bonded monolayers are formed that recline parallel to the Au surface. Stronger interactions with Cu resulted in chemisorption and robust films, with nit8 and nit9 exhibiting upright orientation due to the amide group acting as an efficient binding anchor. Conversely, TEMPO binds to Cu necessarily via NO which is observed to lead to the destruction of the spin-carrying NO functionality. Computational evidence highlighted the decisive role of Cu surface defects in the partial fragmentation of the CONH2 anchor upon chemisorption of nit8 and nit9. Nitroxide radicals' adsorption mechanisms and film properties tunable by appropriately selecting the substrate.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10305 - Fluids and plasma physics (including surface physics)
Result continuities
Project
<a href="/en/project/LM2023072" target="_blank" >LM2023072: Surface Physics Laboratory – Hydrogen Technology Centre</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Materials Chemistry C
ISSN
2050-7526
e-ISSN
2050-7534
Volume of the periodical
12
Issue of the periodical within the volume
19
Country of publishing house
GB - UNITED KINGDOM
Number of pages
14
Pages from-to
6985-6998
UT code for WoS article
001210824000001
EID of the result in the Scopus database
2-s2.0-85192491756