Controlling spins in adsorbed molecules by a chemical switch

Wäckerlin, Christian; Chylarecka, Dorota; Kleibert, Armin; Müller, Kathrin; Iacoviță, Cristian; Nolting, F.; Jung, Thomas A.; Ballav, Nirmalya

doi:10.1038/ncomms1057

Cited by 240 publications

(276 citation statements)

References 38 publications

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“…The molecular spin states in this 2D supramolecular layer can be reversibly manipulated by the on-surface coordination with an external NH 3 ligand. Distinctive responses of NH 3 ligation to MnPc and FeF 16 Pc allowed selective control of the molecular spin states of the Mn or Fe ions. The coordination of NH 3 via its lone pair modified the ligand field of the Fe ion in such way that it yielded a lowspin configuration (S = 0, quenching of the Fe-XMCD signal was observed), while for the MnPc, the NH 3 ligation did not quench the spin but could merely modify it (different Mn-XMCD peak shape compared to the native system).…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

“…The coordination of NH 3 via its lone pair modified the ligand field of the Fe ion in such way that it yielded a lowspin configuration (S = 0, quenching of the Fe-XMCD signal was observed), while for the MnPc, the NH 3 ligation did not quench the spin but could merely modify it (different Mn-XMCD peak shape compared to the native system). Lowtemperature STM (∼78 K) experiments enabled visualization of the coordination of NH 3 to both MnPc and FeF 16 Pc molecules. Interestingly, upon increasing the sample temperature to ∼130 K, the NH 3 ligands were only found on the MnPc molecules, which suggests a relatively higher affinity of NH 3 to MnPc, in comparison to FeF 16 Pc.…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

“…Lowtemperature STM (∼78 K) experiments enabled visualization of the coordination of NH 3 to both MnPc and FeF 16 Pc molecules. Interestingly, upon increasing the sample temperature to ∼130 K, the NH 3 ligands were only found on the MnPc molecules, which suggests a relatively higher affinity of NH 3 to MnPc, in comparison to FeF 16 Pc. Overall, the power of molecular self-assembly can be combined with on-surface coordination chemistry, and thereby, we can explore and exploit the fabrication of novel chemically addressable 2D supramolecular spin-arrays.…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

“…The interrelation between the FM substrate ligand and the axial ligand bound to the on-top site has been referred to as the surface spin-trans effect. 16,17 This Perspective aims at discussing …”

mentioning

confidence: 99%

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Emergence of On-Surface Magnetochemistry

Ballav

Wäckerlin

Siewert

et al. 2013

J. Phys. Chem. Lett.

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The control of exchange coupling across the molecule−substrate interface is a key feature in molecular spintronics. This Perspective reviews the emerging field of on-surface magnetochemistry, where coordination chemistry is applied to surface-supported metal porphyrins and metal phthalocyanines to control their magnetic properties. The particularities of the surface as a multiatomic ligand or "surface ligand" are introduced. The asymmetry involved in the action of a chemical ligand and a surface ligand on the same planar complexes modifies the well-established "trans effect" to the notion of the "surface-trans effect". As ad-complexes on ferromagnetic substrates are usually exchange-coupled, the magnetochemical implications of the surface-trans effect are of particular interest. The combined action of the different ligands allows for the reproducible control of spin states in on-surface supramolecular architectures and opens up new ways toward building and operating spin systems at interfaces. Notably, spin-switching has been demonstrated to be controlled collectively via the interaction with a ligand (chemical selectivity) and individually via local addressing at the interface.A century ago, Alfred Werner laid the foundation of modern coordination chemistry, an achievement for which he was awarded the Nobel Prize in Chemistry in 1913. The innovative concept of primary and secondary valences in coordination complexes that he introduced has since then developed into oxidation states and coordination numbers and become textbook knowledge for introductory chemistry. 1 Briefly, the transition-metal ion in a given coordination complex with a fixed oxidation state can be either diamagnetic or paramagnetic, depending on the number of the ligands as well as their nature. It is the ligands that are responsible for the splitting of the d orbitals of the metal ion into t 2g and e g levels, which are at the heart of ligand field theory (LFT). 1 Thereby, ligand coordination directly alters the magnetic properties. Among the existing coordination complexes, particularly spin-bearing four-coordinated square-planar porphyrins and phthalocyanines have received much attention during the last six decades. Here, the coordination number of the metal ion and hence its magnetic properties can be easily modified by coordination with external axial ligands leading to five/six-fold coordination complexes. 2 Recently, on-surface coordination chemistry of metal porphyrins and metal phthalocyanines has raised increasing attention. 3−5 In this field of research, coordination chemistry of the planar molecules is studied in the presence of a surface ligand and an optional axial ligand binding to the free on-top site. A central issue is whether the known gas-phase coordination chemistry concepts remain valid for ligand coordination of spin-bearing planar metal−organic molecules assembled on (magnetic) surfaces. Emerging evidence shows that due to the surface−molecule interaction, novel magnetochemical effects arise beyond those known...

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Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Emergence of On-Surface Magnetochemistry

Ballav

Wäckerlin

Siewert

et al. 2013

J. Phys. Chem. Lett.

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“…

The development of a variety of nanoscale applications 1, 2 requires the fabrication and control of atomic [3][4][5] or molecular switches 6, 7 that can be reversibly operated by light 8 , a short range force 9, 10 , electric current 11,12 or some other external stimulus [13][14][15] . In order for such molecules to be used as electronic components, they should be directly Fig.

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mentioning

confidence: 99%

A surface-anchored molecular four-level conductance switch based on single proton transfer

et al. 2011

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Emergence of Multispinterface and Antiferromagnetic Molecular Exchange Bias via Molecular Stacking on a Ferromagnetic Film

Byun

Lee

et al. 2020

Adv Funct Materials

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Heterointerfaces may exhibit unexpected physical properties distinct from intrinsic properties of component materials. In particular, metal–organic interfaces can drive unique interfacial spin moments, which are often called molecular spinterface. Here, van der Waals stacking of molecular layers may lead to variations in the intra/interlayer exchange coupling resulting in multiple ground states, which is highly desired for multifunctional magnetic devices. In this report, the emergence of molecular multispinterface of paramagnetic cobalt‐octaethyl‐porphyrin (CoOEP) layers in a Fe/CoOEP heterostructure is demonstrated through the interfacial layer and a successive antiferromagnetic molecular spin chain. The disentangled interfacial ferromagnetic spins lead to multiple magnetic ground states and behave as additional spin‐dependent scattering centers, as evidenced through the magnetotransport study. In addition, the antiferromagnetic molecule spin chain derives tunable exchange bias, which signifies the dominance of the antiferromagnetic interfacial interaction. Theoretical calculations demonstrate spin configurations of the molecular chain and the antiferromagnetic interfacial coupling through oxygen intermediaries. The development of the molecular multispinterface and controllable exchange bias therein will provide a promising route for the active control of multivalued data processing at the nanoscale.

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Controlling spins in adsorbed molecules by a chemical switch

Cited by 240 publications

References 38 publications

Emergence of On-Surface Magnetochemistry

Emergence of On-Surface Magnetochemistry

A surface-anchored molecular four-level conductance switch based on single proton transfer

Emergence of Multispinterface and Antiferromagnetic Molecular Exchange Bias via Molecular Stacking on a Ferromagnetic Film

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