Advances on the nanostructuration of magnetic molecules on surfaces: the case of single-molecule magnets (SMM)

Gómez-Segura, Jordi; Veciana, Jaume; Ruiz‐Molina, Daniel

doi:10.1039/b616352a

Cited by 106 publications

(48 citation statements)

References 66 publications

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“…Depending on the chosen benzoate, 1D (smectic) or 3D (body‐centered cubic) organized mesophases were indeed induced. This is, to the best of our knowledge, the first example of liquid crystalline metallaclusters and as such opens new perspectives in the field of self‐organized and ordered structures of SMMs 11…”

Section: Methodsmentioning

confidence: 73%

Single‐Molecule Magnets with Mesomorphic Lamellar Ordering

et al. 2007

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Single-molecule magnets (SMMs) are materials that are able to retain magnetization at the molecular level below a certain temperature, known as the blocking temperature. [1, 2] These compounds currently elicit sustained research activity: as quantum objects they are envisioned as qubits for quantum computers, and their magnetic properties make them the ultimate storage bits of a molecular magnetic memory. Schematically, these hybrid molecules are made from metal ions bound together by various organic ligands, and numerous types of compounds have been reported to show SMM behavior: 4f coordination compounds, [3] polymetallic cages, [4] and oxometallaclusters. [2,5] Despite its poor stability against water and temperature, the so-called "Mn 12 " compound [Mn 12 O 12 (OAc) 16 (H 2 O) 4 ] is probably the most studied SMM for at least two reasons: its synthesis is cheap and easy, and it long held the record for the highest blocking temperature.[2b]The use of functional molecules in macroscopic devices (bottom-up technology) requires that some degree of lowdimensionality self-organization (1D or 2D) is imparted to the molecules. It is well known that self-organization can only take place in a system that has some fluidity during the process so that positioning errors can be corrected automatically. Liquid crystals are a prime example of molecular assemblies in which order coexists with fluidity. [6] We describe herein how dedicated design can endow the Mn 12 molecule with liquid-crystalline (LC) properties while preserving the peculiar magnetic properties of the original core; a side effect of this added functionality is much improved thermal stability. The formation of positionally ordered mesophases is a first step on the route to organizing SMMs for their eventual incorporation in a functional nanodevice.To counterbalance the a priori unfavorable molecular shape and bulkiness of the Mn 12 cluster core and the important geometrical constraints, we applied the strategies used to obtain thermotropic mesophases with fullerenes (fulleromesogens [7] ), bulky lanthanidomesogens, [8] octahedral coordination complexes, [9] or supramolecular objects.[10] The procedure consists of covalent grafting of either a mesomorphic promoter onto the inorganic cluster through a flexible aliphatic spacer [7, 8b, 10] or strongly lipophilic ligands [8a, 9] to improve interfaces and areas compatibilities between both moieties and to enhance microsegregation.Mesomorphic, dodecanuclear manganese complexes [Mn 12 O 12 (O 2 CR) 16 (H 2 O) 4 ] were thus obtained by the replacement of the 16 LC-inert acetate groups (R = Me) with gallatederived moieties (Scheme 1). Depending on the chosen benzoate, 1D (smectic) or 3D (body-centered cubic) organized mesophases were indeed induced. This is, to the best of our knowledge, the first example of liquid crystalline metallaclusters and as such opens new perspectives in the field of self-organized and ordered structures of SMMs.[ (OAc) 16 ] was prepared in situ from MnOAc 2 and KMnO 4 , and the gal...

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Section: Methodsmentioning

confidence: 73%

Single‐Molecule Magnets with Mesomorphic Lamellar Ordering

et al. 2007

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“…Several approaches to the nanostructuring of SMMs have recently been reviewed, [7][8][9] including their association on surfaces, 7,8 as well as their incorporation into carbon-nanotubes 10,11 and mesoporous silicas. Several approaches to the nanostructuring of SMMs have recently been reviewed, [7][8][9] including their association on surfaces, 7,8 as well as their incorporation into carbon-nanotubes 10,11 and mesoporous silicas.…”

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confidence: 99%

Metal–Organic Frameworks as Platforms for the Controlled Nanostructuring of Single-Molecule Magnets

et al. 2015

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The prototypical single-molecule magnet (SMM) molecule [Mn12O12(O2CCH3)16(OH2)4] was incorporated under mild conditions into a highly porous metal-organic framework (MOF) matrix as a proof of principle for controlled nanostructuring of SMMs. Four independent experiments revealed that the SMM clusters were successfully loaded in the MOF pores, namely synchrotron-based powder diffraction, physisorption analysis, and in-depth magnetic and thermal analyses. The results provide incontrovertible evidence that the magnetic composite, SMM@MOF, combines key SMM properties with the functional properties of MOFs. Most importantly, the incorporated SMMs exhibit a significantly enhanced thermal stability with SMM loading advantageously occurring at the periphery of the bulk MOF crystals with only a single SMM molecule isolated in the transverse direction of the pores.

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“…Various approaches to the nanostructuration of SMMs have recently been reviewed [53] and will therefore not be detailed hereafter. Rather, we shall review recent magnetic and structural characterization results obtained by SQUID and X-ray magnetic circular dichroism (XMCD).…”

Section: Reviewmentioning

confidence: 99%

The Quest for Nanoscale Magnets: The example of [Mn12] Single Molecule Magnets

et al. 2009

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Recent advances on the organization and characterization of [Mn12] single molecule magnets (SMMs) on a surface or in 3D are reviewed. By using nonconventional techniques such as X-ray magnetic circular dichroism (XMCD) and scanning tunneling microscopy (STM), it is shown that [Mn12]-based SMMs deposited on a surface lose their SMM behavior, even though the molecules seem to be structurally undamaged. A new approach is reported to get high-density information-storage devices, based on the 3D assembling of SMMs in a liquid crystalline phase. The 3D nanostructure exhibits the anisotropic character of the SMMs, thus opening the way to address micrometric volumes by two photon absorption using the pump-probe technique. We present recent developments such as µ-SQUID, magneto-optical Kerr effect (MOKE), or magneto-optical circular dichroism (MOCD), which enable the characterization of SMM nanostructures with exceptional sensitivity. Further, the spin-polarized version of the STM under ultrahigh vacuum is shown to be the key tool for addressing not only single molecule magnets, but also magnetic nano-objects.

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Advances on the nanostructuration of magnetic molecules on surfaces: the case of single-molecule magnets (SMM)

Cited by 106 publications

References 66 publications

Single‐Molecule Magnets with Mesomorphic Lamellar Ordering

Single‐Molecule Magnets with Mesomorphic Lamellar Ordering

Metal–Organic Frameworks as Platforms for the Controlled Nanostructuring of Single-Molecule Magnets

The Quest for Nanoscale Magnets: The example of [Mn12] Single Molecule Magnets

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