Valence electronic structure of sublimated Fe<sub>4</sub>single-molecule magnets: an experimental and theoretical characterization

Ninova, Silviya; Lanzilotto, Valeria; Malavolti, Luigi; Rigamonti, Luca; Cortigiani, Brunetto; Mannini, Matteo; Totti, Federico; Sessoli, Roberta

doi:10.1039/c4tc01647e

Cited by 27 publications

(24 citation statements)

References 51 publications

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“…The average g-pitch angle deviates of about 1.5% for both Opt models. 16 Nevertheless, our results show the good transferability of the U parameters within the Fe 4 class of SMMs. We employ the same successful approach used to calculate these properties for the X-ray structures of the Fe 4 family, as reported in our previous paper.…”

Section: Bulk Structural and Magnetic Propertiesmentioning

confidence: 58%

“…These values were taken from the studies by Ninova and Malavolti et al 16,17 Spin moments for the iron ions have been calculated and are reported in Table S5 of the ESI † for the different functionals used. Once the eigenket of the Heisenberg Hamiltonian (eqn (1)) |aSM S i has been evaluated by numerical diagonalization, d S i and d S ij could be calculated taking advantage of the Wigner-Eckart theorem.…”

Section: Calculation Of Magnetic Propertiesmentioning

confidence: 99%

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Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

et al. 2015

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The computational characterization of the single molecule magnet (SMM) [Fe 4 (AcS(CH 2 ) 5 C(CH 2 O) 3 ) 2 (dpm) 6 ] (Fe 4 C 5 ) with Ac = CH 3 CO and Hdpm = dipivaloylmethane, grafted on the Au(111) surface (Fe 4 C 5 @Au (111)) is presented. For the first time, ab initio molecular dynamics (AIMD) calculations have been used to study the evolution of the structural properties of a SMM once adsorbed on a metallic substrate. Important structural rearrangements induced by the grafting process can be observed thanks to the AIMD approach. This allows us to elucidate some possible mechanisms that govern the SMM's magnetism on a surface, which wouldn't be revealed by the standard static approach. The sampling of the SMM@Au(111)'s configurational space at finite temperature, together with magneto-structural correlations, makes it possible to study the fluctuation amplitude of magnetic properties, thus revealing that a single minimum of the free energy surface (FES) is populated at 200 K. Starting from the finite temperature scenario, the potential energy surface (PES) was sampled by means of thermal annealing calculations showing that multiple local minima could be populated at 0 K. Both isotropic exchange coupling constants and zero field splitting (ZFS) parameters are calculated for the identified Fe 4 C 5 @Au(111) local minima, thereby allowing an in-depth characterization of the Fe 4 C 5 magnetic properties from the isolated to the grafted scenario. The cutting-edge computational protocol used here shows that the experimentally observed retention of a spin S = 5 ground state upon grafting results from balancing the major modifications on spin Hamiltonian (SH) parameters. The electronic effects of the metal on the magnetic properties of Fe 4 C 5 have been also discussed.

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Section: Bulk Structural and Magnetic Propertiesmentioning

confidence: 58%

Section: Calculation Of Magnetic Propertiesmentioning

confidence: 99%

Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

et al. 2015

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“…Sublimation has been observed up to now only in the case of 3 Ph [87] and its partially fluorinated variants , . Such systems start to efficiently sublimate in UHV conditions above 450 K, as shown by analyzing the collected deposit with different techniques, including mass spectrometry, AC susceptometry and spectroscopic tools , , , . However, a careful investigation by scanning tunneling microscopy (STM) showed that submonolayers of 3 Ph grown on gold and Cu 2 N/Cu(100) substrates comprise both intact Fe 4 molecules and smaller molecular entities in contact with the surface .…”

Section: Towards Single Molecule Addressing Of Fe4 and Related Systemsmentioning

confidence: 99%

Propeller‐Shaped Fe₄ and Fe₃M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules

et al. 2019

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This Microreview covers the preparation and investigation of Fe 4 and Fe 3 M complexes with a propeller-like structure, most of which function as single-molecule magnets (SMMs). The magnetic characterization of these highly symmetric and chemically versatile complexes has enabled the establishment of important magneto-structural correlations regarding magnetic anisotropy and magnetic relaxation mechanisms in SMM materials. Their chemical stability and easy functionali- [a]

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“…In general, clusters of this family feature easy axis anisotropy normal to the metal plane. Despite the low energy barrier of Fe 4 SMMs reaching up to 15-17 K, their chemical versatility has been exploited by creating clusters able to sublimate by fluorination of the peripheral β-diketonato ligands [15][16][17] or anchor on gold surfaces by sulfur-rich tripodal ligands [18,19], as well as modulating the spin ground state by selective replacement of the central metal ion with chromium(III) [20,21], vanadium(III) [22], or lanthanide ions [23,24]. This family of SMMs has been also characterized as single-molecule junction in scanning tunneling microscope (STM) experiments at 0.5 K [25] and through theoretical calculations for its behavior in spin-polarized transport [26], revealing how Fe 4 SMMs would be excellent candidates for molecular spintronics devices.…”

Section: Introductionmentioning

confidence: 99%

New Silver(I) Coordination Polymer with Fe4 Single-Molecule Magnets as Long Spacer

et al. 2018

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In continuation of our work on supramolecular architectures of single-molecule magnets (SMMs) as a promising strategy in developing their magnetic performance, in this paper we report the synthesis and single crystal X-ray structure of the centered triangular tetrairon(III) SMM, [Fe4(PhpPy)2(dpm)6], Fe4 (Hdpm = dipivaloylmethane, H3PhpPy = 2-(hydroxymethyl)-2-(4-(pyridine-4-yl)phenyl)propane-1,3-diol), and its assembly in the coordination polymer {[Fe4(PhpPy)2(dpm)6Ag](ClO4)}n, Fe4Ag, upon reaction with silver(I) perchlorate. Thanks to the presence of the pyridyl rings on the two tripodal ligands, Fe4 behaves as divergent ditopic linker, and due to the Fe4:AgClO4 1:1 ratio, Fe4Ag probably possesses a linear arrangement in which silver(I) ions are linearly coordinated by two nitrogen atoms, forming 1D chains whose positive charge is balanced by the perchlorate anions. The stabilization of such a polymeric structure can be ascribed to the long distance between the two donor nitrogen atoms (23.4 Å) and their donor power. Fe4Ag shows slow relaxation of the magnetization which follows a thermally activated process with Ueff/kB = 11.17(18) K, τ0 = 2.24(17) 10−7 s in zero field, and Ueff/kB = 14.49(5) K, τ0 = 3.88(8) 10−7 s in 1-kOe applied field, in line with what reported for tetrairon(III) SMMs acting as building blocks in polymeric structures.

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Valence electronic structure of sublimated Fe₄single-molecule magnets: an experimental and theoretical characterization

Cited by 27 publications

References 51 publications

Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

Propeller‐Shaped Fe₄ and Fe₃M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules

New Silver(I) Coordination Polymer with Fe4 Single-Molecule Magnets as Long Spacer

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Valence electronic structure of sublimated Fe4single-molecule magnets: an experimental and theoretical characterization

Cited by 27 publications

References 51 publications

Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

Single molecule magnets grafted on gold: magnetic properties from ab initio molecular dynamics

Propeller‐Shaped Fe4 and Fe3M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules

New Silver(I) Coordination Polymer with Fe4 Single-Molecule Magnets as Long Spacer

Contact Info

Product

Resources

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Valence electronic structure of sublimated Fe₄single-molecule magnets: an experimental and theoretical characterization

Propeller‐Shaped Fe₄ and Fe₃M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules