We present a theoretical and experimental study of two tetracoordinate Co(II)-based complexes with semi-coordination interactions, i.e., non-covalent interactions involving the central atom. We argue that such interactions enhance the thermal and structural stability of the compounds, making them appropriate for deposition on substrates, as demonstrated by their successful deposition on graphene. DC magnetometry and high-frequency electron spin resonance (HF-ESR) experiments revealed an axial magnetic anisotropy and weak intermolecular antiferromagnetic coupling in both compounds, supported by theoretical predictions from complete active space self-consistent field calculations complemented by N-electron valence state second-order perturbation theory (CASSCF-NEVPT2), and broken-symmetry density functional theory (BS-DFT). AC magnetometry demonstrated that the compounds are field-induced single-ion magnets (SIMs) at applied static magnetic fields, with slow relaxation of magnetization governed by a combination of quantum tunneling, Orbach, and direct relaxation mechanisms. The structural stability under ambient conditions and after deposition was confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Theoretical modeling by DFT of different configurations of these systems on graphene revealed n-type doping of graphene originating from electron transfer from the deposited molecules, confirmed by electrical transport measurements and Raman spectroscopy.

Central European Institute of Technology CEITEC BUT Purkyňova 656 123 61200 Brno Czech Republic

Department of Inorganic Chemistry Faculty of Chemical and Food Technology Slovak University of Technology in Bratislava Bratislava SK 81237 Slovakia

Department of Inorganic Chemistry Faculty of Science Palacký University 17 listopadu 12 77147 Olomouc Czech Republic

Department of Physics Georgetown University Washington DC USA

Institute of Physical Engineering Faculty of Mechanical Engineering Brno University of Technology Technická 2 61669 Brno Czech Republic

Institute of Physics of Materials Czech Academy of Sciences Žižkova 22 61662 Brno Czech Republic

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