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1.
J Am Chem Soc ; 144(27): 12520-12535, 2022 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-35759747

RESUMO

The molecular wheel [Cr10(OMe)20(O2CCMe3)10], abbreviated {Cr10}, with an unusual intermediate total spin S = 9 and non-negligible cluster anisotropy, D/kB = -0.045(2) K, is a rare case among wheels based on an even number of 3d-metals, which usually present an antiferromagnetic (AF) ground state (S = 0). Herein, we unveil the origin of such a behavior. Angular magnetometry measurements performed on a single crystal confirmed the axial anisotropic behavior of {Cr10}. For powder samples, the temperature dependence of the susceptibility plotted as χT(T) showed an overall ferromagnetic (FM) behavior down to 1.8 K, whereas the magnetization curve M(H) did not saturate at the expected 30 µB/fu for 10 FM coupled 3/2 spin Cr3+ ions, but to a much lower value, corresponding to S = 9. In addition, the X-ray magnetic circular dichroism (XMCD) measured at high magnetic field (170 kOe) and 7.5 K showed the polarization of the cluster moment up to 23 µB/fu. The magnetic results can be rationalized within a model, including the cluster anisotropy, in which the {Cr10} wheel is formed by two semiwheels, each with four Cr3+ spins FM coupled (JFM/kB = 2.0 K), separated by two Cr3+ ions AF coupled asymmetrically (J23/kB = J78/kB = -2.0 K; J34/kB = J89/kB = -0.25 K). Inelastic neutron scattering and heat capacity allowed us to confirm this model leading to the S = 9 ground state and first excited S = 8. Single-molecule magnet behavior with an activation energy of U/kB = 4.0(5) K in the absence of applied field was observed through ac susceptibility measurements down to 0.1 K. The intriguing magnetic behavior of {Cr10} arises from the detailed asymmetry in the molecule interactions produced by small-angle distortions in the angles of the Cr-O-Cr alkoxy bridges coupling the Cr3+ ions, as demonstrated by ab initio and density functional theory calculations, while the cluster anisotropy can be correlated to the single-ion anisotropies calculated for each Cr3+ ion in the wheel.

2.
J Am Chem Soc ; 140(7): 2504-2513, 2018 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-29373020

RESUMO

Magnetic exchange interactions within the asymmetric dimetallic compounds [hqH2][Ln2(hq)4(NO3)3]·MeOH, (Ln = Er(III) and Yb(III), hqH = 8-hydroxyquinoline) have been directly probed with EPR spectroscopy and accurately modeled by spin Hamiltonian techniques. Exploitation of site selectivity via doping experiments in Y(III) and Lu(III) matrices yields simple EPR spectra corresponding to isolated Kramers doublets, allowing determination of the local magnetic properties of the individual sites within the dimetallic compounds. CASSCF-SO calculations and INS and far-IR measurements are all employed to further support the identification and modeling of the local electronic structure for each site. EPR spectra of the pure dimetallic compounds are highly featured and correspond to transitions within the lowest-lying exchange-coupled manifold, permitting determination of the highly anisotropic magnetic exchange between the lanthanide ions. We find a unique orientation for the exchange interaction, corresponding to a common elongated oxygen bridge for both isostructural analogs. This suggests a microscopic physical connection to the magnetic superexchange. These results are of fundamental importance for building and validating model microscopic Hamiltonians to understand the origins of magnetic interactions between lanthanides and how they may be controlled with chemistry.

3.
Inorg Chem ; 56(21): 12839-12847, 2017 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-28984447

RESUMO

CeCuAl3 crystallizing in the tetragonal BaNiSn3-type structure and CeCuxAl4-x solid solutions were investigated by means of elastic and inelastic neutron scattering. Powder neutron diffraction brought information on both temperature evolution of crystallographic parameters and magnetic order at low temperatures. No structural change was observed in the investigated temperature range from 1.5 to 300 K. Weak magnetic peaks outside nuclear Bragg positions observed in solid solutions with 0.90 ≤ x ≤ 1.10 were described by the propagation vector k = (0.40 + δx, 0.60 + δy, 0), where δx ≈ 0.02 and δy ≈ 0.01. The magnetic structure of CeCu0.75Al3.25 consists of two components: an anti-ferromagnetic one described by the same k and a ferromagnetic one with k0 = (0, 0, 0) and magnetic moments lying within the tetragonal basal plane. The evolution of magnetic excitations as a function of Cu-Al concentration in CeCuxAl4-x was studied by inelastic neutron scattering. The measured spectra of CeCuAl3 and the solution with x = 0.95 point to a three-magnetic-peak energy scheme, while only two excitations are expected from the local symmetry conditions on Ce atoms. The standard two-peak spectrum of crystal electric field excitations was observed for Cu-Al substitutions further from the 1:1:3 stoichiometry (x = 0.75 and 1.10). The intermediate concentrations (x = 0.90 and 1.05) exhibit spectra on the border between the former cases with a less clear pronounced first inelastic magnetic peak. The observed behavior is discussed considering the evolution of structural parameters in the CeCuxAl4-x system and the coupling between the lattice vibrations and the crystal electric field excitations.

4.
Chemistry ; 22(5): 1779-88, 2016 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-26748964

RESUMO

The spin dynamics of Cr8 Mn, a nine-membered antiferromagnetic (AF) molecular nanomagnet, are investigated. Cr8 Mn is a rare example of a large odd-membered AF ring, and has an odd-number of 3d-electrons present. Odd-membered AF rings are unusual and of interest due to the presence of competing exchange interactions that result in frustrated-spin ground states. The chemical synthesis and structures of two Cr8 Mn variants that differ only in their crystal packing are reported. Evidence of spin frustration is investigated by inelastic neutron scattering (INS) and muon spin relaxation spectroscopy (µSR). From INS studies we accurately determine an appropriate microscopic spin Hamiltonian and we show that µSR is sensitive to the ground-spin-state crossing from S=1/2 to S=3/2 in Cr8 Mn. The estimated width of the muon asymmetry resonance is consistent with the presence of an avoided crossing. The investigation of the internal spin structure of the ground state, through the analysis of spin-pair correlations and scalar-spin chirality, shows a non-collinear spin structure that fluctuates between non-planar states of opposite chiralities.

5.
Angew Chem Int Ed Engl ; 55(31): 8856-9, 2016 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-27294807

RESUMO

The first regular homometallic ring containing an odd number of metal centers is reported. The ring was synthesized by means of amine-templated self-assembly. Extensive physical characterization studies, including magnetic measurements, powder inelastic neutron scattering (INS), and DFT calculations, show that the molecule has a near perfect match to the expected behavior for a frustrated system with the lowest energy pair of S=1/2 spin states separated by only 0.1 meV (0.8 cm(-1) ).

6.
Proc Natl Acad Sci U S A ; 109(47): 19113-8, 2012 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-23132941

RESUMO

The term "frustration" in the context of magnetism was originally used by P. W. Anderson and quickly adopted for application to the description of spin glasses and later to very special lattice types, such as the kagomé. The original use of the term was to describe systems with competing antiferromagnetic interactions and is important in current condensed matter physics in areas such as the description of emergent magnetic monopoles in spin ice. Within molecular magnetism, at least two very different definitions of frustration are used. Here we report the synthesis and characterization of unusual nine-metal rings, using magnetic measurements and inelastic neutron scattering, supported by density functional theory calculations. These compounds show different electronic/magnetic structures caused by frustration, and the findings lead us to propose a classification for frustration within molecular magnets that encompasses and clarifies all previous definitions.

7.
J Am Chem Soc ; 136(27): 9763-72, 2014 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-24968057

RESUMO

Compounds of general formula [Cr7MF3(Etglu)(O2C(t)Bu)15(Phpy)] [H5Etglu = N-ethyl-d-glucamine; Phpy = 4-phenylpyridine; M = Zn (1), Mn (2), Ni (3)] have been prepared. The structures contain an irregular octagon of metal sites formed around the penta-deprotonated Etglu(5-) ligand; the chirality of N-ethyl-d-glucamine is retained in the final product. The seven Cr(III) sites have a range of coordination environments, and the divalent metal site is crystallographically identified and has a Phpy ligand attached to it. By using complementary experimental techniques, including magnetization and specific heat measurements, inelastic neutron scattering, and electron paramagnetic resonance spectroscopy, we have investigated the magnetic features of this family of {Cr7M} rings. Microscopic parameters of the spin Hamiltonian have been determined as a result of best fits of the different experimental data, allowing a direct comparison with corresponding parameters found in the parent compounds. We examine whether these parameters can be transferred between compounds and compare them with those of an earlier family of heterometallic rings.

8.
Phys Rev E ; 105(5-1): 054603, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35706300

RESUMO

In this paper a combined neutron scattering and quantum simulation study of the collective dynamics in liquid Ne-D_{2} mixtures, at a temperature of T=30K and in the wave-vector transfer range 4 nm^{-1}

9.
Sci Rep ; 11(1): 18640, 2021 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-34545134

RESUMO

Disorder-disorder phase transitions are rare in nature. Here, we present a comprehensive low-temperature experimental and theoretical study of the heat capacity and vibrational density of states of 1-fluoro-adamantane (C10H15F), an intriguing molecular crystal that presents a continuous disorder-disorder phase transition at T = 180 K and a low-temperature tetragonal phase that exhibits fractional fluorine occupancy. It is shown that fluorine occupancy disorder in the low-T phase of 1-fluoro-adamantane gives rise to the appearance of low-temperature glassy features in the corresponding specific heat (i.e., "boson peak" -BP-) and vibrational density of states. We identify the inflation of low-energy optical modes as the main responsible for the appearance of such glassy heat-capacity features and propose a straightforward correlation between the first localized optical mode and maximum BP temperature for disordered molecular crystals (either occupational or orientational). Thus, the present study provides new physical insights into the possible origins of the BP appearing in disordered materials and expands the set of molecular crystals in which "glassy-like" heat-capacity features have been observed.

10.
J Phys Chem Lett ; 12(36): 8826-8832, 2021 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-34491740

RESUMO

We discuss a cost-effective approach to understand magnetic relaxation in the new generation of rare-earth single-molecule magnets. It combines ab initio calculations of the crystal field parameters, of the magneto-elastic coupling with local modes, and of the phonon density of states with fitting of only three microscopic parameters. Although much less demanding than a fully ab initio approach, the method gives important physical insights into the origin of the observed relaxation. By applying it to high-anisotropy compounds with very different relaxation, we demonstrate the power of the approach and pinpoint ingredients for improving the performance of single-molecule magnets.

11.
Nat Commun ; 11(1): 942, 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-32071303

RESUMO

Low thermal conductivity is favorable for preserving the temperature gradient between the two ends of a thermoelectric material, in order to ensure continuous electron current generation. In high-performance thermoelectric materials, there are two main low thermal conductivity mechanisms: the phonon anharmonic in PbTe and SnSe, and phonon scattering resulting from the dynamic disorder in AgCrSe2 and CuCrSe2, which have been successfully revealed by inelastic neutron scattering. Using neutron scattering and ab initio calculations, we report here a mechanism of static local structure distortion combined with phonon-anharmonic-induced ultralow lattice thermal conductivity in α-MgAgSb. Since the transverse acoustic phonons are almost fully scattered by the compound's intrinsic distorted rocksalt sublattice, the heat is mainly transported by the longitudinal acoustic phonons. The ultralow thermal conductivity in α-MgAgSb is attributed to its atomic dynamics being altered by the structure distortion, which presents a possible microscopic route to enhance the performance of similar thermoelectric materials.

14.
Chem Sci ; 9(14): 3555-3562, 2018 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-29780487

RESUMO

The Cr7Co ring represents a model system to understand how the anisotropy of a CoII ion is transferred to the effective anisotropy of a polymetallic cluster by strong exchange interactions. Combining sizeable anisotropy with exchange interactions is an important point in the understanding and design of new anisotropic molecular nanomagnets addressing fundamental and applicative issues. By combining electron paramagnetic resonance and inelastic neutron scattering measurements with spin Hamiltonian and ab initio calculations, we have investigated in detail the anisotropy of the CoII ion embedded in the antiferromagnetic ring. Our results demonstrate a strong and anisotropic exchange interaction between the Co and the neighbouring Cr ions, which effectively transmits the anisotropy to the whole molecule.

15.
Rev Sci Instrum ; 82(3): 034101, 2011 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-21456765

RESUMO

Inelastic neutron scattering (INS) is increasingly being used for the characterization of heterogeneous catalysts. As the technique is uniquely sensitive to hydrogen atoms, vibrational spectra can be obtained that emphasize a hydrogenous component or hydrogen-containing moieties adsorbed on to an inorganic support. However, due to sensitivity constraints, the technique typically requires large sample masses (∼10 g catalyst). A reaction system is hereby described that enables suitable quantities of heterogeneous catalysts to be appropriately activated and operated under steady-state conditions for extended periods of time prior to acquisition of the INS spectrum. In addition to ex situ studies, a cell is described which negates the need for a sample transfer stage between reaction testing and INS measurement. This cell can operate up to temperatures of 823 K and pressures up to 20 bar. The apparatus is also amenable to adsorption experiments at the gas-solid interface.

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