We demonstrate that Fe4 molecules can be deposited on gold by thermal sublimation in ultra-high vacuum with retention of single molecule magnet behavior. A magnetic hysteresis comparable to that found in bulk samples is indeed observed when a submonolayer film is studied by X-ray magnetic circular dichroism. Scanning tunneling microscopy evidences that Fe4 molecules are assembled in a two-dimensional lattice with short-range hexagonal order and coexist with a smaller contaminant. The presence of intact Fe4 molecules and the retention of their bistable magnetic behavior on the gold surface are supported by density functional theory calculations.
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http://dx.doi.org/10.1021/nl503925h | DOI Listing |
Chem Sci
September 2024
Department of Chemistry, Carnegie Mellon University Pittsburgh PA 15213 USA
Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe]) clusters based on a multidentate ligand platform (L) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (butylamino)pyrazolate ligand (PzNH Bu). These clusters bear a terminal Fe(iii)-O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center a μ-oxido ligand.
View Article and Find Full Text PDFACS Nano
July 2024
Institute of Chemistry, University of Potsdam, 14476 Potsdam, Germany.
The detection of a single-enzyme catalytic reaction by surfaced-enhanced Raman scattering (SERS) is presented by utilizing DNA origami-based plasmonic antennas. A single horseradish peroxidase (HRP) was accommodated on a DNA origami nanofork plasmonic antenna (DONA) containing gold nanoparticles, enabling the tracing of single-molecule SERS signals during the peroxide reduction reaction. This allows monitoring of the structure of a single enzymatic catalytic center and products under suitable liquid conditions.
View Article and Find Full Text PDFNanoscale
August 2024
Department of Chemistry "U. Schiff" - DICUS - and INSTM Research Unit, University of Florence, Via della Lastruccia 3-13, 50019 Sesto Fiorentino, FI, Italy.
The decoration of technologically relevant surfaces, such as metal oxides, with Single-Molecule Magnets (SMMs) constitutes a persistent challenge for the integration of these molecular systems into novel technologies and, in particular, for the development of spintronic and quantum devices. We used UHV thermal sublimation to deposit tetrairon(III) propeller-shaped SMMs (Fe) as a single layer on a TiO ultrathin film grown on Cu(001). The properties of the molecular deposit were studied using a multi-technique approach based on standard topographic and spectroscopic measurements, which demonstrated that molecules remain largely intact upon deposition.
View Article and Find Full Text PDFSmall Methods
September 2024
Division of New Energy Materials, Institute of Zhejiang University-Quzhou, Quzhou, 324000, China.
Designing a multifunctional electrocatalyst to produce H from water, urea, urine, and wastewater, is highly desirable yet challenging because it demands precise Fermi-engineering to realize stronger π-donation from O 2p to electron(e)-deficient metal (t) d-orbitals. Here a Sr-induced phase transformed β-FeOOH/α-Ni(OH) catalyst anchored on Ni-foam (designated as pt-NFS) is introduced, where Sr produces plenteous Fe (Fe → Fe) to modulate Fermi level and e-transfer from e-rich Ni(t)-orbitals to e-deficient Fe(t)-orbitals, via strong π-donation from the π-symmetry lone-pair of O bridge. pt-NFS utilizes Fe-sites near the Sr-atom to break the H─O─H bonds and weakens the adsorption of *O while strengthening that of *OOH, toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2023
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden.
Nitrogenases take nitrogen from the air and reduce it to ammonia. It has long been known that N becomes activated after four reductions in the catalytic cycle, in the E state. Several mechanisms for the activation have been suggested.
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