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Inorg Chem ; 2020 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-32196322


Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.

Chemistry ; 25(69): 15846-15857, 2019 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-31529652


Large separations between ground and excited magnetic states in single-molecule magnets (SMMs) are desirable to reduce the likelihood of spin reversal in the molecules. Spin-phonon coupling is a process leading to magnetic relaxation. Both the reversal and coupling, making SMMs lose magnetic moments, are undesirable. However, direct determination of large magnetic states separations (>45 cm-1 ) is challenging, and few detailed investigations of the spin-phonon coupling have been conducted. The magnetic separation in [Co(12-crown-4)2 ](I3 )2 (12-crown-4) (1) is determined and its spin-phonon coupling is probed by inelastic neutron scattering (INS) and far-IR spectroscopy. INS, using oriented single crystals, shows a magnetic transition at 49.4(1.0) cm-1 . Far-IR reveals that the magnetic transition and nearby phonons are coupled, a rarely observed phenomenon, with spin-phonon coupling constants of 1.7-2.5 cm-1 . The current work spectroscopically determines the ground-excited magnetic states separation in an SMM and quantifies its spin-phonon coupling, shedding light on the process causing magnetic relaxation.

Nat Commun ; 9(1): 2572, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29968702


Spin-phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1-2 cm-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin-phonon couplings in typical transition metal complexes and sheds light on the origin of the spin-phonon entanglement.

J Am Chem Soc ; 137(40): 12923-8, 2015 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26352187


The high-spin (S = 1) tetrahedral Ni(II) complex [Ni{(i)Pr2P(Se)NP(Se)(i)Pr2}2] was investigated by magnetometry, spectroscopic, and quantum chemical methods. Angle-resolved magnetometry studies revealed the orientation of the magnetization principal axes. The very large zero-field splitting (zfs), D = 45.40(2) cm(-1), E = 1.91(2) cm(-1), of the complex was accurately determined by far-infrared magnetic spectroscopy, directly observing transitions between the spin sublevels of the triplet ground state. These are the largest zfs values ever determined--directly--for a high-spin Ni(II) complex. Ab initio calculations further probed the electronic structure of the system, elucidating the factors controlling the sign and magnitude of D. The latter is dominated by spin-orbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.

ACS Appl Mater Interfaces ; 7(22): 12080-8, 2015 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-25988364


Here, we report the photoconducting response of field-effect transistors based on three atomic layers of chemical vapor transport grown WSe2 crystals mechanically exfoliated onto SiO2. We find that trilayered WSe2 field-effect transistors, built with the simplest possible architecture, can display high hole mobilities ranging from 350 cm(2)/(V s) at room temperature (saturating at a value of ∼500 cm(2)/(V s) below 50 K) displaying a strong photocurrent response, which leads to exceptionally high photoresponsivities up to 7 A/W under white light illumination of the entire channel for power densities p < 10(2) W/m(2). Under a fixed wavelength of λ = 532 nm and a laser spot size smaller than the conducting channel area, we extract photoresponsitivities approaching 100 mA/W with concomitantly high external quantum efficiencies up to ∼40% at room temperature. These values surpass values recently reported from more complex architectures, such as graphene and transition metal dichalcogenides based heterostructures. Also, trilayered WSe2 phototransistors display photoresponse times on the order of 10 µs. Our results indicate that the addition of a few atomic layers considerably decreases the photoresponse times, probably by minimizing the interaction with the substrates, while maintaining a very high photoresponsivity.