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Evidence for efficient anchoring in nitroxyl radical thin films: an experimental XPS/NEXAFS and theoretical DFT/TD-DFT study.

Authors :
Totani, Roberta
Ljubić, Ivan
Mehl, Sascha L.
Kalinovych, Viacheslav
Jugovac, Matteo
Bonano, Gabriele
Ciavardini, Alessandra
Grazioli, Cesare
Galdenzi, Federico
D'Addato, Sergio
de Simone, Monica
Sheverdyaeva, Polina M.
Moras, Paolo
Tsud, Nataliya
Coreno, Marcello
Source :
Journal of Materials Chemistry C; 5/21/2024, Vol. 12 Issue 19, p6985-6998, 14p
Publication Year :
2024

Abstract

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 CONH<subscript>2</subscript> anchor upon chemisorption of nit8 and nit9. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
20507526
Volume :
12
Issue :
19
Database :
Complementary Index
Journal :
Journal of Materials Chemistry C
Publication Type :
Academic Journal
Accession number :
177294712
Full Text :
https://doi.org/10.1039/d4tc00427b