Large orbital moment of two coupled spin-half Co ions in a complex on gold

The magnetic properties of transition-metal ions are generally described by the atomic spins of the ions and their exchange coupling. The orbital moment, usually largely quenched due the ligand field, is then seen as a perturbation. In such a scheme, S = 1/2 ions are predicted to be isotropic. We investigate a Co(II) complex with two antiferromagnetically coupled 1/2 spins on Au(111) using low-temperature scanning tunneling microscopy, X-ray magnetic circular dichroism, and density functional theory. We find that each of the Co ions has an orbital moment comparable to that of the spin, leading to magnetic anisotropy, with the spins preferentially oriented along the Co–Co axis. The orbital moment and the associated magnetic anisotropy is tuned by varying the electronic coupling of the molecule to the substrate and the microscope tip. These findings show the need to consider the orbital moment even in systems with strong ligand fields. As a consequence, the description of S = 1/2 ions becomes strongly modified, which have important consequences for these prototypical systems for quantum operations.We acknowledge financial support from the European Union’s Horizon 2020 program, grant number 766726. C.L. thanks the Alexander von Humboldt Foundation for a Research Fellowship for Postdoctoral Researchers and also acknowledges support from Kiel Nano, Surface and Interface Science (KiNSIS). M.G. acknowledges funding from the Deutsche Forschungsgemeinschaft (DFG; Project-ID 278162697 - CRC 1242, Project A08). R.R. and N.L. acknowledge financial support from the European Union project ESiM 101046364 and the Spanish State Research Agency grant (Project No. PID2021-127917NB-I00) funded by MCIN/AEI/10.13039/50110001103; they are grateful for the computer resources at Finisterrae II and the technical support provided by CESGA. Views and opinions expressed are however those of the authors only and do not necessarily reflect those of the European Union. Neither the European Union nor the granting authority can be held responsible for them. Centro de Química Estrutural (CQE) and Institute of Molecular Sciences (IMS) acknowledge the financial support of Fundação para a Ciência e Tecnologia (FCT) (Projects UIDB/00100/2020, UIDP/00100/2020, and LA/P/0056/2020, respectively). P.N.M. and S.Re. thank FTC for the research contracts CEEC-IND/00509/2017 and 2020.02134.CEECIND. S.Ru. acknowledges funding from the Swiss National Science Foundation (grant number 200021_175941).Peer reviewe