Aza-Triangulene: On-Surface Synthesis and Electronic and Magnetic Properties

Nitrogen heteroatom doping into a triangulene molecule allows tuning its magnetic state. However, the synthesis of the nitrogen-doped triangulene (aza-triangulene) has been challenging. Herein, we report the successful synthesis of aza-triangulene on the Au(111) and Ag(111) surfaces, along with thei...

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Veröffentlicht in:Journal of the American Chemical Society 2022-03, Vol.144 (10), p.4522-4529
Hauptverfasser: Wang, Tao, Berdonces-Layunta, Alejandro, Friedrich, Niklas, Vilas-Varela, Manuel, Calupitan, Jan Patrick, Pascual, Jose Ignacio, Peña, Diego, Casanova, David, Corso, Martina, de Oteyza, Dimas G
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Sprache:eng
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Zusammenfassung:Nitrogen heteroatom doping into a triangulene molecule allows tuning its magnetic state. However, the synthesis of the nitrogen-doped triangulene (aza-triangulene) has been challenging. Herein, we report the successful synthesis of aza-triangulene on the Au(111) and Ag(111) surfaces, along with their characterizations by scanning tunneling microscopy and spectroscopy in combination with density functional theory (DFT) calculations. Aza-triangulenes were obtained by reducing ketone-substituted precursors. Exposure to atomic hydrogen followed by thermal annealing and, when necessary, manipulations with the scanning probe afforded the target product. We demonstrate that on Au(111), aza-triangulene donates an electron to the substrate and exhibits an open-shell triplet ground state. This is derived from the different Kondo resonances of the final aza-triangulene product and a series of intermediates on Au(111). Experimentally mapped molecular orbitals match with DFT-calculated counterparts for a positively charged aza-triangulene. In contrast, aza-triangulene on Ag(111) receives an extra electron from the substrate and displays a closed-shell character. Our study reveals the electronic properties of aza-triangulene on different metal surfaces and offers an approach for the fabrication of new hydrocarbon structures, including reactive open-shell molecules.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c12618