Assembly of Ferrocene Molecules on Metal Surfaces Revisited

Ormaza, Maider; Abufager, Paula; Bachellier, Nicolas; Robles, Roberto; Vérot, Martin; Bahers, Tangui Le; Bocquet, Marie‐Laure; Lorente, Nicolás; Limot, L.

doi:10.1021/jz5026118

Cited by 48 publications

(65 citation statements)

References 36 publications

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“…This ring is moreover tilted approximately by 11 • with respect to the surface normal ( Fig.5c) due to the packing of the molecules. 39 Note that if the Co atom were on top the Fc molecule, according to simulated images (not shown here) no ring-like shape would be observed in the STM images.…”

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confidence: 61%

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On-Surface Engineering of a Magnetic Organometallic Nanowire

et al. 2015

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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.

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confidence: 61%

“…[36][37][38] The ring-shape tip apex corresponds to a Cp ring of a tilted Fc molecule. 39 Placing this molecular tip on top of the Co atom and proceeding the same way, i. e., decreasing the tip-sample distance until a certain threshold value, we are able to release the molecule from the tip. reactive CoFc species.…”

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On-Surface Engineering of a Magnetic Organometallic Nanowire

et al. 2015

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“…In the molecular network, however, these "vertically" adsorbed molecules coexist with "horizontally" adsorbed molecules (principal axis parallel to the surface), as sketched in the inset of Fig. 1 This T-shaped configuration is governed by van der Waals interactions [23] and results in two possible molecular configurations, known as paired [ Fig. 1(a)] and compact (not shown) [22].…”

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Vibron-assisted spin excitation in a magnetically anisotropic molecule

et al. 2020

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The ability to electrically-drive spin excitations in molecules with magnetic anisotropy is key for high-density storage and quantum-information technology. Electrons, however, also tunnel via the vibrational excitations unique to a molecule. The interplay of spin and vibrational excitations offers novel routes to study and, ultimately, electrically manipulate molecular magnetism. Here we use a scanning tunneling microscope to electrically induce spin and vibrational excitations in a single molecule consisting of a nickelocene magnetically coupled to a Ni atom. We evidence a vibron-assisted spin excitation at an energy one order of magnitude higher compared to the usual spin excitations of nickelocene and explain it using first-principles calculations that include electron correlations. Furthermore, we observe that spin excitations can be quenched by modifying the Ni-nickelocene coupling. Our study suggests that nickelocene-based complexes constitute a model playground for exploring the interaction of spin and vibrations in the electron transport through single magnetic molecules.Magnetic molecules are potential candidates for information-storing technology [1], molecular spintronics [2] and quantum computing [3], provided that their axial magnetic anisotropy DS 2 z ensures a magnetic bistability among longlived magnetic states. But molecules also vibrate. In particular, in magnetic molecules the interplay of vibrational modes, or vibrons, with the spin degrees of freedom is known to impact the spin lifetime [4][5][6]. Since vibrational modes can couple to the electric charge, producing vibron-assisted electron excitations in transport [7][8][9], expectations are that similar effects should be also observed with the electronic spin [10,11].Concerning this last point, experimental work has predominantly focused on a well-known spin-related manybody effect, the Kondo effect. The electron-vibron interaction in Kondo molecules was shown to produce satellite Kondo resonances in the differential conductance spectra at the bias of the vibron's excitation energy [12][13][14]. These resonances were ascribed to tunneling electrons that have their spin flipped when elastically scattering off the molecular spin, but with sufficient energy to activate a vibrational mode in the molecule [15]. The question arises whether a similar mechanism is also possible with other spin scattering mechanisms that magnetically excite a molecule such as inelastic scattering involving magnetic anisotropy [16]. These so-called spin excitations show great potential in view of an all-electrical manipulation of the molecular spin [17,18].Here, we use scanning tunneling microscopy (STM) to demonstrate the presence of a combined vibrational-spin excitation in a single nickelocene molecule [Ni(C 5 H 5 ) 2 , see Fig. 1(d); noted Nc hereafter] coupled to a Ni atom. Nickelocene is a spin S = 1 molecule of the metallocene family with magnetic anisotropy, where spin excitations produce a sizable increase of the electronic transport [19]. We show that the o...

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“…Molecules in two adjacent rows adsorbed with a tilt of about 10 ̊ with respect to each other [17]. However, both vertical and horizontal adsorption geometries of ferrocene molecules were observed on Cu (100) and Cu (111) substrates [18]. Nevertheless, the adsorption behavior and stable geometry of ferrocene molecule on surfaces is still limited.…”

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confidence: 99%

Adsorption mechanism of ferrocene molecule on pristine and functionalized graphene

Nigar

Wang

Imtiaz

et al. 2019

Applied Surface Science

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The adsorption behavior and stable geometries of ferrocene molecule on pristine, oxygen and hydroxyl functionalized graphene surfaces are investigated by using first principle density functional calculations based on the PBE-D2 method, which uses GGA-PBE functional with the incorporation of van der Waals (VDW) forces. Our calculations reveal that on all graphene substrates (pristine, oxygen and hydroxyl functionalized), the ferrocene molecule adsorbed with its molecular axis parallel to the surface. Oxygen and hydroxyl functionalized graphene systems have higher adsorption energies, higher charge transfer values and shorter adsorption heights as compared to the pristine graphene. It is concluded that sandwich type π-π interaction along with the van der Waals forces plays a major role in these adsorptions. The physisorption of ferrocene

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Assembly of Ferrocene Molecules on Metal Surfaces Revisited

Abstract: The posting must be for non-commercial purposes and not violate the ACS' "Ethical Guide. This version is published under a "All rights reserved" license.

Cited by 48 publications

References 36 publications

On-Surface Engineering of a Magnetic Organometallic Nanowire

On-Surface Engineering of a Magnetic Organometallic Nanowire

Vibron-assisted spin excitation in a magnetically anisotropic molecule

Adsorption mechanism of ferrocene molecule on pristine and functionalized graphene

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