On-Surface Engineering of a Magnetic Organometallic Nanowire

Abstract

The manipulation of the molecular spin state by atom doping is an attractive strategy to confer desirable magnetic properties to molecules. Here, we present the formation of novel magnetic metallocenes by following this approach. In particular, two different on-surface procedures to build isolated and layer-integrated Co-ferrocene (CoFc) molecules on a metallic substrate via atomic manipulation and atom deposition are shown. The structure as well as the electronic properties of the so-formed molecule are investigated combining scanning tunneling microscopy and spectroscopy with density functional theory calculations. It is found that unlike single ferrocene a CoFc molecule possesses a magnetic moment as revealed by the Kondo effect. These results correspond to the first controlled procedure toward the development of tailored metallocene-based nanowires with a desired chemical composition, which are predicted to be promising materials for molecular spintronics.

Engineering hybrid Co-picene structures with variable spin coupling

“…The increase in q factor from 0.2 for the Co atom to 33 for CoPc corresponds to the change in Fano lineshape from the dip-like resonance feature to the peak-like one, which may be ascribed to the enhanced coupling of the STM tip to the Co atom in the case of CoPc due to new coupling channel via the orbital hybridizations between the Co d orbitals and the Pc molecular orbitals, similar to previous studies on the metal-molecule complex. 28,30,35 More interestingly, we note that the lineshape of the dI/dV spectra measured at both Co sites of Co 2 Pc in Fig. 2(g) is similar to that in CoPc and can be fitted by Fano function with the same C K and q parameters, indicating that the magnetic coupling between the two magnetic centers in Co 2 Pc is negligible.…”

“…[25][26][27] Alternatively, the STM atom/molecule manipulation can be used as an effective method to construct new metal-molecule hybrid structures and to engineer the magnetism. 28 To achieve this goal, a facile approach is to bond a given molecule to individual magnetic atoms one by one with STM manipulation, and then probe their magnetism by STS. In this study, we show that picene (Pc), a planar polycyclic aromatic hydrocarbon molecule, can be manipulated to accommodate multiple magnetic Co atoms and form stable magnetic hybrid Co x Pc structures, x ¼ 1, 2, and 3.…”

Controlled spin switching in a metallocene molecular junction

“…The spin transition takes place due to the enhanced electronic screening following the Nc-surface contact. On a more general note, the portability of the Nc molecule or eventually of other metallocenes 59 via the STM tip offers novel opportunities for testing how surface-supported objects modify the molecular magnetism of these molecules.…”

Toward an automated analysis of exchange pathways in spin‐coupled systems

“…For atoms, the Ruderman–Kittel–Kasuya–Yoshida (RKKY) mechanism is typically dominant, in which the coupling between the local spins is mediated by the conduction electrons of the metal. However, for molecules with multiple spin centers or supramolecular arrangements of spin‐polarized molecules on surfaces, the situation is less clear, since RKKY interactions are expected to be in competition with the spin coupling mediated by bridging ligands in the molecule (Fig. , bottom).…”