Abstract
Starting from a long aza-starphene neutral and nonmagnetic organic molecule, a single-molecule magnet is on-surface constructed using up to 3 light nonmagnetic aluminum (Al) atoms. Seldom observed in solution with transition-metal atoms and going from 1 to 3 Al coordinated atoms, the doublet-singlet-doublet transition is easily on-surface accessible using the scanning tunneling microscope single-atom and single-molecule manipulations on a gold(111) surface. With 3 coordinated Al atoms, the lateral vibration modes of the Al3-aza-starphene molecule magnet are largely frozen. Using the Kondo states, this opens the observation of the in-phase Al vertical atom vibrations and out-of-phase central phenyl vibrations.
Highlights
Starting from a long aza-starphene neutral and nonmagnetic organic molecule, a single-molecule magnet is onsurface constructed using up to 3 light nonmagnetic aluminum (Al) atoms
O n-surface coordination chemistry uses various metals (Au, Ag, Cu, Fe, etc.) and ligands, resulting in the formation of different coordination complexes as compared to solution chemistry.1−3 For example, a 3-fold coordination is typically encountered using a single Au adatom on a Au(111) metal surface,4 but not in solution.5−7 For a light nontransition-metal atom-like aluminum, we have recently demonstrated that its oxidation state on a Au(111) surface is between Al(I) and Al(II), leading to the on-surface formation of a magnetic molecule after coordinating two Al adatoms to a tetrabenzophenazine nonmagnetic molecule
Going a step further in intramolecular spin frustration and ordering, a doubletsinglet-doublet magnetic transition is observed in solution for only a few organometallic complexes when coordinating not two but three d electron transition-metal atoms
Summary
Letter vibration modes of the Alx−HATA molecule complexes (1) Stepanow, S.; Lin, N.; Payer, D.; Schlickum, U.; Klappenberger,. Surface-Assisted Assembly of 2D Metal−Organic Networks That Exhibit Unusual Threefold Coordination Symmetry. Organometallics Completely Revised and Extended, 3rd ed.; WILEY-VCH Verlag GmbH & Co. KGaA: Weinheim, 2006. (4) Nakanishi, W.; Nakata, A.; Perez, P.; Takeuchi, M.; Joachim, C.; Toulouse, France; International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Material Sciences (NIMS), Ibaraki 305-0044, Japan; orcid.org/0000-0003-2081-4039; Email: we-hyo.soe@ cemes.fr Roberto Robles − Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), 20018 Donostia-San Sebastián, Spain; orcid.org/0000-0001-7808-0395; Sagisaka, K. (5) Stepanow, S.; Lin, N.; Payer, D.; Schlickum, U.; Klappenberger, F.; Zoppellaro, G.; Ruben, M.; Brune, H.; Barth, J. Surface-Assisted Assembly of 2D Metal−Organic Networks That. Authors Paula de Mendoza − Institute of Chemical Research of Assembled Metal−Organic Networks. 6808-3007 Nicolas Lorente − Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), 20018 Donostia-San Sebastián, Spain;.
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