Francesco Pineider

Magnetic memory of a single-molecule quantum magnet wired to a gold surface

In the field of molecular spintronics, the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. Although simple paramagnetic molecules can show surface-induced magnetic ordering and hysteresis when deposited on ferromagnetic surfaces, information storage at the molecular level requires molecules exhibiting an intrinsic remnant magnetization, like the so-called single-molecule magnets (SMMs). These have been intensively investigated for their rich quantum behaviour but no magnetic hysteresis has been so far reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, we have now found that robust, tailor-made Fe(4) complexes retain magnetic hysteresis at gold surfaces. Our results demonstrate that isolated SMMs can be used for storing information. The road is now open to address individual molecules wired to a conducting surface in their blocked magnetization state, thereby enabling investigation of the elementary interactions between electron transport and magnetism degrees of freedom at the molecular scale.

Quantum tunnelling of the magnetization in a monolayer of oriented single-molecule magnets

A fundamental step towards atomic- or molecular-scale spintronic devices has recently been made by demonstrating that the spin of an individual atom deposited on a surface, or of a small paramagnetic molecule embedded in a nanojunction, can be externally controlled. An appealing next step is the extension of such a capability to the field of information storage, by taking advantage of the magnetic bistability and rich quantum behaviour of single-molecule magnets (SMMs). Recently, a proof of concept that the magnetic memory effect is retained when SMMs are chemically anchored to a metallic surface was provided. However, control of the nanoscale organization of these complex systems is required for SMMs to be integrated into molecular spintronic devices. Here we show that a preferential orientation of Fe4 complexes on a gold surface can be achieved by chemical tailoring. As a result, the most striking quantum feature of SMMs—their stepped hysteresis loop, which results from resonant quantum tunnelling of the magnetization—can be clearly detected using synchrotron-based spectroscopic techniques. With the aid of multiple theoretical approaches, we relate the angular dependence of the quantum tunnelling resonances to the adsorption geometry, and demonstrate that molecules predominantly lie with their easy axes close to the surface normal. Our findings prove that the quantum spin dynamics can be observed in SMMs chemically grafted to surfaces, and offer a tool to reveal the organization of matter at the nanoscale.

XAS and XMCD Investigation of Mn12 Monolayers on Gold

The deposition of Mn(12) single molecule magnets on gold surfaces was studied for the first time using combined X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) methods at low temperature. The ability of the proposed approach to probe the electronic structure and magnetism of Mn(12) complexes without significant sample damage was successfully checked on bulk samples. Detailed information on the oxidation state and magnetic polarization of manganese ions in the adsorbates was obtained from XAS and XMCD spectra, respectively. Partial reduction of metal ions to Mn(II) was clearly observed upon deposition on Au(111) of two different Mn(12) derivatives bearing 16-acetylthio-hexadecanoate and 4-(methylthio)benzoate ligands. The average oxidation state, as well as the relative proportions of Mn(II), Mn(III) and Mn(IV) species, are strongly influenced by the deposition protocol. Furthermore, the local magnetic polarizations are significantly decreased as compared with bulk Mn(12) samples. The results highlight an utmost redox instability of Mn(12) complexes at gold surfaces, presumably accompanied by structural rearrangements, which cannot be easily revealed by standard surface analysis based on X-ray photoelectron spectroscopy and scanning tunnelling microscopy.

Magnetic Poles Determinations and Robustness of Memory Effect upon Solubilization in a DyIII-Based Single Ion Magnet

The [Dy(tta)3(L)] complex behaves as a single ion magnet both in its crystalline phase and in solution. Experimental and theoretical magnetic anisotropy axes perfectly match and lie along the most electro-negative atoms of the coordination sphere. Both VSM and MCD measurements highlight the robustness of the complex, with persistence of the memory effect even in solution up to 4 K.

Circular magnetoplasmonic modes in gold nanoparticles.

The quest for efficient ways of modulating localized surface plasmon resonance is one of the frontiers in current research in plasmonics; the use of a magnetic field as a source of modulation is among the most promising candidates for active plasmonics. Here we report the observation of magnetoplasmonic modes on colloidal gold nanoparticles detected by means of magnetic circular dichroism (MCD) spectroscopy and provide a model that is able to rationalize and reproduce the experiment with unprecedented qualitative and quantitative accuracy. We believe that the steep slope observed at the plasmon resonance in the MCD spectrum can be very efficient in detecting changes in the refractive index of the surrounding medium, and we give a simple proof of principle of its possible implementation for magnetoplasmonic refractometric sensing.

Coexistence of plasmonic and magnetic properties in Au89Fe11 nanoalloys

We describe an environmentally friendly, top-down approach to the synthesis of Au89Fe11 nanoparticles (NPs). The plasmonic response of the gold moiety and the magnetism of the iron moiety coexist in the Au89Fe11 nanoalloy with strong modification compared to single element NPs, revealing a non-linear surface plasmon resonance dependence on the iron fraction and a transition from paramagnetic to a spin-glass state at low temperature. These nanoalloys are accessible to conjugation with thiolated molecules and they are promising contrast agents for magnetic resonance imaging.

Erratic magnetic hysteresis of TbPc2 molecular nanomagnets

Terbium(III) bis-phthalocyaninato neutral complex, a robust and evaporable Single Molecule Magnet (SMM) with a record height of the anisotropy barrier, has recently attracted a great interest as an active unit in single molecule electronics, but at the same time its magnetic hysteresis has been found to be strongly affected when the environment is different from the crystalline phase. Here we present a systematic investigation of the magnetization dynamics in different environments, obtained by magnetic dilution, thermal treatment and sublimation of the molecules, to shed some light on the origin of the evanescence of the hysteretic behavior of this unique SMM.

Spin-Polarization Transfer in Colloidal Magnetic-Plasmonic Au/Iron Oxide Hetero-nanocrystals

We report on the unprecedented direct observation of spin-polarization transfer across colloidal magneto-plasmonic Au@Fe-oxide core@shell nanocrystal heterostructures. A magnetic moment is induced into the Au domain when the magnetic shell contains a reduced Fe-oxide phase in direct contact with the noble metal. An increased hole density in the Au states suggested occurrence of a charge-transfer process concomitant to the magnetization transfer. The angular to spin magnetic moment ratio, m(orb)/m(spin), for the Au 5d states, which was found to be equal to 0.38, appeared to be unusually large when compared to previous findings. A mechanism relying on direct hybridization between the Au and Fe states at the core/shell interface is proposed to account for the observed transfer of the magnetic moment.

Grafting Single Molecule Magnets on Gold Nanoparticles

The chemical synthesis and characterization of the first hybrid material composed by gold nanoparticles and single molecule magnets (SMMs) are described. Gold nanoparticles are functionalized via ligand exchange using a tetrairon(III) SMM containing two 1,2-dithiolane end groups. The grafting is evidenced by the shift of the plasmon resonance peak recorded with a UV-vis spectrometer, by the suppression of nuclear magnetic resonance signals, by X-ray photoemission spectroscopy peaks, and by transmission electron microscopy images. The latter evidence the formation of aggregates of nanoparticles as a consequence of the cross-linking ability of Fe4 through the two 1,2-dithiolane rings located on opposite sides of the metal core. The presence of intact Fe4 molecules is directly proven by synchrotron-based X-ray absorption spectroscopy and X-ray magnetic circular dichroism spectroscopy, while a detailed magnetic characterization, obtained using electron paramagnetic resonance and alternating-current susceptibility, confirms the persistence of SMM behavior in this new hybrid nanostructure.

Laser generation of iron-doped silver nanotruffles with magnetic and plasmonic properties

A frontier topic in nanotechnology is the realization of multifunctional nanoparticles (NPs) via the appropriate combination of different elements of the periodic table. The coexistence of Fe and Ag in the same nanostructure, for instance, is interesting for nanophotonics, nanomedicine, and catalysis. However, alloying of Fe and Ag is inhibited for thermodynamic reasons. Here, we describe the synthesis of Fe-doped Ag NPs via laser ablation in liquid solution, bypassing thermodynamics constraints. These NPs have an innovative structure consisting of a scaffold of face-centered cubic metal Ag alternating with disordered Ag–Fe alloy domains, all arranged in a truffle-like morphology. The Fe–Ag NPs exhibit the plasmonic properties of Ag and the magnetic response of Fe-containing phases, and the surface of the Fe–Ag NPs can be functionalized in one step with thiolated molecules. Taking advantage of the multiple properties of Fe–Ag NPs, the magnetophoretic amplification of plasmonic properties is demonstrated with proof-of-concept surface-enhanced Raman scattering and photothermal heating experiments. The synthetic approach is of general applicability and virtually permits the preparation of a large variety of multi-element NPs in one step.