Naslov
Self-assembly and interactions of aromatic C- nitroso derivatives on Au(111) surface: from nitroso monolayers to azodioxy polymer films

Autori
Nuić, Laura ; Panić, Barbara ; Šrut Rakić, Iva ; Kralj, Marko ; Vančik, Hrvoj ; Biljan, Ivana

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, neobjavljeni rad, znanstveni

Skup
Self-Assembly and Supramolecular Chemistry Gordon Research Conference

Mjesto i datum
Les Diablerets, Švicarska, 14.05.2023. - 19.05.2023

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
aromatski C-nitrozo spojevi, nitrozo monoslojevi, azodioksidni polimerni filmovi
(aromatic C-nitroso compounds, nitoso monolayers, azodioxide polymer films)

Sažetak
Adsorption of organic molecules on metal surfaces and their arrangements into ordered self-assembled monolayers (SAMs) and/or multilayers offers a way for the design of functional materials with wide potential applications. Surface properties of SAMs can be finely tuned by incorporation of various terminal groups which can be used to link specific molecules or nanostructures. The ability of aromatic C-nitroso compounds to dimerize or polymerize to azodioxides provides the possibility for the controlled fabrication of bilayer or multilayer films by interactions of nitroso groups at the monolayer interface and those free in solution through azodioxy bonds. Due to the photochromic and thermochromic behavior of the azodioxy/nitroso system in the solid state, the disassembly and reassembly of the azodioxy bonds in the films could be externally controlled by UV radiation and heat. Recently, it has been shown that compounds containing aromatic dinitroso moiety, which enables the formation of azodioxy oligomers or polymers, have interesting electronic properties [1], and their incorporation into azodioxy films could be used for the construction of organic electronic devices. Our previous studies showed that the adsorption of nitrosobenzene derivatives, functionalized with sulfur headgroups, on Au(111) surface results in the formation of nitroso monolayers and azodioxy bilayers [2-5]. High-resolution scanning tunneling microscopy (STM) revealed that within monolayers and bilayers molecules are arranged into hexagonal structures [2]. In the first part of this study, we investigated the polymerization of structurally different aromatic dinitroso compounds initiated by nitroso- terminated monolayer on Au(111) surface, which could result in the formation of azodioxy polymer thin films. Azodioxy films were prepared by immersing the modified Au(111) substrate, to which the monolayer of the aromatic mononitroso derivative was previously attached through the S– Au bond [2, 5], in a solution of the corresponding dinitroso derivative. After the substrate was removed from the solution, thoroughly rinsed with a solvent and dried, the produced films were characterized by ellipsometry, atomic force microscopy (AFM) and nanoscale Fourier transform infrared (nano-FTIR) spectroscopy. The obtained results indicated formation of azodioxy oligomer films composed of only a few monomeric subunits or the possible tilting and intertwining of the oligomeric chains within the films resulting in poorly organized surface structures [6]. It was also found that the formation of azodioxy oligomers on Au(111) surface is more pronounced with longer adsorption times. The second part of this study deals with the synthesis and self- assembly of new aromatic C- nitroso compounds with or without an alkyl side chain and containing disulfide headgroup for adsorption on gold. The self-assembly behavior of the synthesized compounds on Au(111) surface was investigated by AFM and STM, and the interrelationship between the molecular and surface structures is discussed. REFERENCES [1] L. Matasović, B. Panić, M. Bubaš, H. Vančik, I. Biljan, I. Rončević, J. Mater. Chem. C 10 (2022) 5433–5446. [2] I. Biljan, M. Kralj, T. Mišić Radić, V. Svetličić, H. Vančik, J. Phys. Chem. C 115 (2011) 20267−20273. [3] I. Biljan, T. Medančić, M. Kralj, T. Mišić Radić, V. Svetličić, H. Vančik, Croat. Chem. Acta 86 (2013) 83-94. [4] T. Klačić, K. Varga, M. Kralj, I. Delač Marion, H. Vančik, I. Biljan, Colloids Surf. A 552 (2018) 110–117. [5] B. Panić, M. Koprivnjak, T. Marić, K. Majerová Varga, I. Biljan, Colloid Interface Sci. Commun. 45 (2021) 100539. ACKNOWLEDGMENTS This work has been fully supported by Croatian Science Foundation under the project IP-2020-02- 4467.

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija

POVEZANOST RADA