Communication: Influence of graphene interlayers on the interaction between cobalt phthalocyanine and Ni(111)

Uihlein, Johannes; Peisert, Heiko; Glaser, Mathias; Polek, Małgorzata; Adler, Hilmar; Petraki, F.; Ovsyannikov, Ruslan; Bauer, Michel; Chassé, Thomas

doi:10.1063/1.4793523

Cited by 31 publications

(49 citation statements)

References 33 publications

(41 reference statements)

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“…This agrees with results of XPS and NEXAFS investigations of CoPc [582] and MnPc [612] on graphene/Ni (1 1 1), for which interfacial charge transfer from the Ni surface through the graphene layer to the complexes was found. Involvement of the d z 2 orbital at the metal center was discussed [582,612]. On graphene/Ru(0 0 0 1), it was found that CoPc couples with its Co d z 2 orbital to the Ru surface, while the Pc ring was decoupled by the graphene layer.…”

Section: Graphene and Boron Nitridesupporting

confidence: 92%

“…From an HREELS study of FePc, CoPc, NiPc, CuPc and ZnPc on graphene/Ni (1 1 1), it was concluded that NiPc, CuPc and ZnPc were completely decoupled from the metal substrate, whereas for FePc and CoPc decoupling was limited to the ligand [585]. This agrees with results of XPS and NEXAFS investigations of CoPc [582] and MnPc [612] on graphene/Ni (1 1 1), for which interfacial charge transfer from the Ni surface through the graphene layer to the complexes was found. Involvement of the d z 2 orbital at the metal center was discussed [582,612].…”

Section: Graphene and Boron Nitridesupporting

confidence: 82%

“…The state at 0.45 eV below E F contained large contributions from Co, whereas the state at 0.1 eV above E F was attributed to the molecular LUMO hybridizing with electronic states of the Cu(1 0 0) surface [581]. Strong substrate interaction, mediated by the d z 2 orbital, and electron transfer to the Co center were also observed on Ni(1 1 1) [582] and Ru(0001) [583]. The interactions of the Co center with these substrates was maintained even when they were separated by a graphene monolayer, as will be discussed in Section 5.1.…”

Section: Cobalt Complexesmentioning

confidence: 80%

“…Graphene and h-BN monolayers between the metal substrate and the adsorbed molecules can lead to a partial electronic decoupling when the metal substrate is weakly interacting, such as Ir(1 1 1) [584,628], whereas substantial residual coupling was observed for more strongly interacting substrates such as Ni(1 1 1) and Ru(0 0 0 1) [582,583,585,[598][599][600]612].…”

Section: Graphene and Boron Nitridementioning

confidence: 93%

See 3 more Smart Citations

Surface chemistry of porphyrins and phthalocyanines

Gottfried

2015

Surface Science Reports

551

584

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Section: Graphene and Boron Nitridesupporting

confidence: 92%

Section: Graphene and Boron Nitridesupporting

confidence: 82%

Section: Cobalt Complexesmentioning

confidence: 80%

Section: Graphene and Boron Nitridementioning

confidence: 93%

See 2 more Smart Citations

Surface chemistry of porphyrins and phthalocyanines

Gottfried

2015

Surface Science Reports

551

584

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“…Additionally, evidence of charge transfer at moleculegraphene-Ni(111) interfaces [15,16] and the theoretical prediction of large charge transfer from cobaltocene (CoCp 2 ) to graphene [17] would suggest that a magnetic coupling between cobaltocene and the Ni(111) surface through the graphene layer is still achievable.…”

mentioning

confidence: 99%

Graphene-mediated exchange coupling between a molecular spin and magnetic substrates

et al. 2013

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Using first-principles calculations we demonstrate sizable exchange coupling between a magnetic molecule and a magnetic substrate via a graphene layer. As a model system we consider cobaltocene (CoCp2) adsorbed on graphene deposited on Ni(111). We find that the magnetic coupling between the molecule and the substrate is antiferromagnetic and varies considerably depending on the molecule structure, the adsorption geometry, and the stacking of graphene on Ni(111). We show how this coupling can be tuned by intercalating a magnetic monolayer, e.g. Fe or Co, between graphene and Ni(111). We identify the leading mechanism responsible for the coupling to be the spatial and energy matching of the frontier orbitals of CoCp2 and graphene close to the Fermi level, and we demonstrate the role of graphene as an electronic decoupling layer, yet allowing spin communication between molecule and substrate.PACS numbers: 71.15. Mb, 75.50.Xx, 81.05.ue The emerging field of organic spintronics capitalizes on the novel functionalities achieved when organic molecules are adsorbed on magnetic substrates. The ability to manipulate and tune these functionalities is an important goal. Several problems remain however, before such systems can be incorporated into new technological devices. One in particular is the capability to adsorb molecules on surfaces without any detrimental effects being caused to either the structural or magnetic properties of the molecule. For this reason it is vital to choose molecules with maximum structural robustness upon adsorption [1][2][3]. To this end, the phthalocyanine and porphyrin families are popular choices due to their planar geometry [4][5][6][7][8][9]. However, in some cases, the strong interaction between the metal ion of such flat molecules and the substrate can modify its electronic states and even quench its magnetic moment [10].The use of non-planer molecules, such as metallocenes, can minimize this effect. Metallocenes are composed of a 3d transition-metal ion sandwiched between two cyclopentadienyls (Cp). Depending on the metal ion species, both non-magnetic and paramagnetic behavior can be found [11]. The spin of the metal ion is shielded from the surface by the cage formed by the two Cp rings, reducing the possibility that it will be modified substantially after adsorption. Unfortunately, the deposition of metallocenes on metallic surfaces is a difficult process [12] and, in some cases, complete dissociation of the molecule occurs [13,14].The intercalation of a graphene spacer layer between the reactive surface and the metallocene can reduce the possibility of molecular dissociation during deposition. Additionally, evidence of charge transfer at moleculegraphene-Ni(111) interfaces [15,16] and the theoretical prediction of large charge transfer from cobaltocene (CoCp 2 ) to graphene [17] would suggest that a magnetic coupling between cobaltocene and the Ni(111) surface through the graphene layer is still achievable.In this Letter, we predict, by first principles electronic structure metho...

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Cobalt Single‐Atom‐Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity

Chen

Liu

et al. 2019

Advanced Materials

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The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long‐standing pursuit in chemical synthesis. A vertically structured, cobalt single atom‐intercalated molybdenum disulfide catalyst (Co1‐in‐MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single‐atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide‐bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high‐value, multifunctional sulfones and late‐stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom‐intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.

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Communication: Influence of graphene interlayers on the interaction between cobalt phthalocyanine and Ni(111)

Cited by 31 publications

References 33 publications

Surface chemistry of porphyrins and phthalocyanines

Surface chemistry of porphyrins and phthalocyanines

Graphene-mediated exchange coupling between a molecular spin and magnetic substrates

Cobalt Single‐Atom‐Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity

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