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

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.