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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 azatriangulene 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 ketonesubstituted 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.

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Scanning probe microscopy makes it possible to image and spectroscopically characterize nanoscale objects, and to manipulate and excite them; even time-resolved experiments are now routinely achieved. This combination of capabilities has enabled proof-of-principle demonstrations of nanoscale devices, including logic operations based on molecular cascades , a single-atom transistor , a single-atom magnetic memory cell and a kilobyte atomic memory . However, a key challenge is fabricating device structures that can overcome their attraction to the underlying surface and thus protrude from the two-dimensional flatlands of the surface. Here we demonstrate the fabrication of such a structure: we use the tip of a scanning probe microscope to lift a large planar aromatic molecule (3,4,9,10-perylenetetracarboxylic-dianhydride) into an upright, standing geometry on a pedestal of two metal (silver) adatoms. This atypical and surprisingly stable upright orientation of the single molecule, which under all known circumstances adsorbs flat on metals, enables the system to function as a coherent single-electron field emitter. We anticipate that other metastable adsorbate configurations might also be accessible, thereby opening up the third dimension for the design of functional nanostructures on surfaces.