Deposition of intact tetrairon(iii) single molecule magnet monolayers on gold: an STM, XPS, and ToF-SIMS investigation

Pineider, Francesco; Mannini, Matteo; Danieli, Chiara; Armelao, Lidia; Piras, Federica M.; Magnani, Agnese; Cornia, Andrea; Sessoli, Roberta

doi:10.1039/b916895h

Cited by 37 publications

(53 citation statements)

References 46 publications

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“…The spectrum is characterized by two peaks centered at 712 and 724 eV, being consistent with the literature. 20 These peak positions are characteristic of Fe(III) 30 and are expected from the chemical structure of the Fe 4 molecule. The XPS spectrum of the SAM after immersion in H 2 O is presented in Fig.…”

Section: Methodsmentioning

confidence: 96%

Effect of Aqueous Environment on Monolayer of Tetrairon(III) Single Molecule Magnet

Kanata

Nishino

Aoki

2012

J. Electrochem. Soc.

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A self-assembled monolayer (SAM) of a single molecule magnet (SMM) bearing a tetrairon(III) core and sulfur-containing terminal groups was exposed to aqueous solution. The effect of the chemical environment on the monolayer was investigated using cyclic voltammetry, X-ray photoelectron spectroscopy, and atomic force microscopy. The physisorbed SMM molecules desorbed and the sulfur atoms in the remaining SMM were oxidized during immersion in H 2 O, while the Fe(III) ions remained intact. We found that the SMM molecules concomitantly formed aggregates on the surface. These transformations caused significant changes to the redox properties of the SMM. The present research highlights the fragile nature of the SMM SAM against particular chemical environments and provides important insights into the exploitation of surface-tethered SMMs for a variety of applications.Single molecule magnets (SMMs) are a unique class of functional molecules. They possess versatile magnetic properties and show rich quantum behavior such as magnetic hysteresis of a molecular origin 1 and quantum tunneling of magnetization. 2 Since the first discovery of molecular magnetism in [Mn 12 (OAc) 16 (H 2 O) 4 O 12 ] (Mn 12 acetate), 3 SMMs have attracted considerable interest because of their potential for information storage device applications. In addition, SMMs offer a peculiar opportunity to explore magnetism at the nanoscale. Because it is desirable to immobilize SMM molecules on a solid surface to utilize and probe their magnetism, many studies have been devoted to create two-dimensional assemblies of SMMs. Several different approaches have been reported to deposit Mn 12 acetate, which is the archetypal SMM, on substrates including stamp-assisted deposition on a Si substrate, 4 immobilization by ligand-exchange on the surfaces of self-assembled monolayers (SAMs), 5-9 and grafting via electrostatic interactions. 10 Moreover, direct deposition onto metal surfaces can be achieved using organosulfur derivatives of Mn 12 acetate. 11-14 It is important to retain the useful magnetic properties for these surfacetethered SMMs. However, it is known that the Mn 12 acetate loses the useful magnetic property on a solid surface due to the structural instability of its inorganic core in the highly strained surface environment. [15][16][17][18] To avoid this, a different class of SMMs featuring tetrairon(III) cores (Fe 4 ) has been developed. It has recently proven that Fe 4 SMMs are sufficiently chemically robust to maintain magnetic hysteresis after direct deposition. 19,20 Besides developing methodology for surface immobilization, the practical application of SMMs requires an understanding of the chemical stability of their surface assembly against various chemical environments. Although the characterization of such stability is very important given the intrinsically fragile nature of SMMs, the available knowledge on this subject is quite limited. Currently the peculiar properties of SMMs emerge only at low temperatures, and this fact hampers their utili...

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Section: Methodsmentioning

confidence: 96%

Effect of Aqueous Environment on Monolayer of Tetrairon(III) Single Molecule Magnet

Kanata

Nishino

Aoki

2012

J. Electrochem. Soc.

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“…Initially, the Fe 4 SMM with long alkyl chains (C9) was successfully anchored on Au surface and retained hysteresis in the magnetization from XMCD [26], but further XPS analysis indicated that the S atoms of either one or both ligands can bind the surface since the alkyl chains are long enough (Fig. 6.7b) [27]. As a result, the anisotropic axes of Fe 4 SMMs were still oriented randomly on the surface.…”

Section: Transition Metal Smms On Au Surfacementioning

confidence: 97%

Conclusion and Perspective

Tang

Zhang

2015

Lanthanide Single Molecule Magnets

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As a new type of lanthanide SMMs, the novel endohedral metallofullerene (EMF) SMMs are introduced in the first part of this chapter. Furthermore, a survey of the organization of SMMs on surfaces and molecular spintronics is provided with an emphasis focusing on the applications of double-decker phthalocyanine lanthanide SMMs in spintronics. Herein, [LnPc 2 ] SMMs were not only used to fabricate three-terminal spin transistor, but its combination with carbon-based nanostructures leaded to the successful design of supramolecular spin valve. Remarkably, the nuclear spin of Tb atom embedded in [TbPc 2 ] SMM can be read out electronically through detecting the conductance jump, indicating the great promise of lanthanide SMMs in future applications.Keywords Endohedral metallofullerene · Au surface · Molecular spintronics · Spin transistor · Spin valve · Nuclear spin Naturally, the ultimate goal of SMM research is to develop future devices for possible applications in information storage and quantum computing. Therefore, now considerable efforts in some research groups have been devoted to the anchoring and organization of SMMs on surfaces as well as the design of molecular spintronics using SMMs. In contrast to traditional magnetic nanoparticles, the magnetic molecular clusters possess a well-defined structure and behave like perfectly monodisperse nanomagnets, which allow us to design a target molecule-based device. Nevertheless, one critical problem is the poor stability against water and temperature for most reported SMMs, especially lanthanide SMMs, and thus developing new type of SMM family is still necessary to obtain feasible SMMs with structural and magnetic stability when anchoring them on surfaces. Undoubtedly, a new era of collaborative research has been starting among synthetic chemists, physicists, and theorists [1]. This chapter will be devoted to this aspect.

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“…Recent attention has been devoted to the deposition of photo-switchable compounds on surfaces and whether their intrinsic properties are retained in thin lms or in individual particles. [51][52][53][54][55][56][57][58][59] Langmuir-Blodgett deposition is another approach that affords a number of advantages when working with moleculebased systems. [34][35][36][37][38][39][40][41][42] These systems sometimes exhibit signicant changes of properties, such as an increase of the relaxation temperature 43 or surface induced magnetic anisoptopy.…”

Section: Introductionmentioning

confidence: 99%

Photomagnetic molecular and extended network Langmuir–Blodgett films based on cyanide bridged molybdenum–copper complexes

Bridonneau¹,

Long²,

Cantin

et al. 2015

RSC Adv.

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Two types of cyanide bridged molybdenum-copper photomagnetic films have been obtained: the first one is based on a molecular [MoCu 6 ] complex, the other being a two-dimensional [MoCu 2 ] coordination network. Both systems employ surfactant functionalized ligands and films were deposited on Melinex substrates using the Langmuir-Blodgett technique. All systems, including monolayer films, showed full retention of the intrinsic photomagnetic properties known for analogous solids as demonstrated by EPR spectroscopy.

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Deposition of intact tetrairon(iii) single molecule magnet monolayers on gold: an STM, XPS, and ToF-SIMS investigation

Cited by 37 publications

References 46 publications

Effect of Aqueous Environment on Monolayer of Tetrairon(III) Single Molecule Magnet

Effect of Aqueous Environment on Monolayer of Tetrairon(III) Single Molecule Magnet

Conclusion and Perspective

Photomagnetic molecular and extended network Langmuir–Blodgett films based on cyanide bridged molybdenum–copper complexes

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