NCAFM2023 Programme Booklet

Tuesday 1200-1220

Federico Frezza, 1 Ana Sánchez-Grande, 1 Sofia Canola, 1 Christophe Nacci, 2 Jan Berger, 1 Daniel Mildner, 1 Pingo Mutombo, 1 Irena G. Stará, 3 Ivo Stary, 3 José Angel Martín-Gago, 4 Leonhard Grill 2 and Pavel Jelínek 1 1 Institute of Physics, Academy of Sciences of the Czech Republic, 16200 Prague 6, Czech Republic 2 Department of Physical Chemistry, Institute of Chemistry, University of Graz, 8010 Graz, Austria 3 Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 16610 Prague 6, Czech Republic 4 Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain. SELF-ASSEMBLY AND CONTROLLED DISSOCIATION OF ORGANIC AZIDES ON AU(111) FOR THE GENERATION OF METAL-STABILIZED NITRENES Organic azides attracted interest as versatile precursors for the synthesis of several nitrogen-containing compounds. In particular, the azide group can be considered as a protective group for nitrogen-centered radicals that play a key role as reaction intermediates in biological and pharmaceutical processes, as well as in the direct synthesis of amines and amides. [1] The high reactivity of azides makes them challenging to study even on surfaces. Our group previously reported the direct aromatic azides transformation on Ag(111), leading to the formation of several products, originated from a common elusive nitrenoid intermediate, chemisorbed on the Ag(111) surface. [2] In this work, we deposit 2,6-diazidoanthracene-9,10-dione molecules on Au(111) under ultra-high vacuum conditions, observing the ordered self-assembly of intact molecules. Scanning probe microscopies at low temperature allow to control the tip-molecule interaction at the nanometric scale. Here, we generate and visualize a metal-stabilized nitrene after inducing the removal of molecular nitrogen (N 2 ) from the azide groups. This dissociation process can be carried out on a single-molecule level through tip manipulation or on a larger scale with UV light irradiation. We characterized the system by STM, STS and nc-AFM supported by DFT calculations. Email: frezza@fzu.cz

Fig. Chemical sketch and nc-AFM images of the self-assembled 2,6-diazidoanthracene-9,10-dione on Au(111) before (left) and after (right) the tip-induced removal of N 2 on both sides of each molecule. Size of nc-AFM images: 6 x 6 nm 2 . References [1] M. Minozzi, D. Nanni, and P. Spagnolo, Chemistry – A European Journal, vol. 15 , no. 32, pp. 7830–7840, 2009 [2] J. Hellerstedt et al., Angewandte Chemie International Edition, vol. 58 , no. 8, pp. 2266–2271, 2019

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