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1.
Phys Chem Chem Phys ; 19(47): 32079-32085, 2017 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-29182175

RESUMEN

Well-defined sized (5-10 nm) metallic iron nanoparticles (NPs) with body-centered cubic structure encapsulated inside the tip of millimeter-long vertically aligned carbon nanotubes (VACNTs) of uniform length have been investigated with high-resolution transmission electron microscopy and soft X-ray spectroscopy techniques. Surface-sensitive and chemically-selective measurements have been used to evaluate the magnetic properties of the encapsulated NPs. The encapsulated Fe NPs display magnetic remanence up to room temperature, low coercivity, high chemical stability and no significant anisotropy. Our surface-sensitive measurements combined with the specific morphology of the studied VACNTs allow us to pinpoint the contribution of the surface oxidized or hydroxidized iron catalysts present at the VACNT-substrate interface.

2.
J Am Chem Soc ; 136(14): 5451-9, 2014 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-24635343

RESUMEN

The spin state of organic-based magnets at interfaces is to a great extent determined by the organic environment and the nature of the spin-carrying metal center, which is further subject to modifications by the adsorbate-substrate coupling. Direct chemical doping offers an additional route for tailoring the electronic and magnetic characteristics of molecular magnets. Here we present a systematic investigation of the effects of alkali metal doping on the charge state and crystal field of 3d metal ions in Cu, Ni, Fe, and Mn phthalocyanine (Pc) monolayers adsorbed on Ag. Combined X-ray absorption spectroscopy and ligand field multiplet calculations show that Cu(II), Ni(II), and Fe(II) ions reduce to Cu(I), Ni(I), and Fe(I) upon alkali metal adsorption, whereas Mn maintains its formal oxidation state. The strength of the crystal field at the Ni, Fe, and Mn sites is strongly reduced upon doping. The combined effect of these changes is that the magnetic moment of high- and low-spin ions such as Cu and Ni can be entirely turned off or on, respectively, whereas the magnetic configuration of MnPc can be changed from intermediate (3/2) to high (5/2) spin. In the case of FePc a 10-fold increase of the orbital magnetic moment accompanies charge transfer and a transition to a high-spin state.


Asunto(s)
Electrones , Indoles/química , Metales Alcalinos/química , Metales Pesados/química , Compuestos Organometálicos/química , Dicroismo Circular , Isoindoles , Microscopía de Túnel de Rastreo , Espectroscopía de Absorción de Rayos X
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