Accurate and unequivocal determination of the crystal-field parameters of lanthanide ions via a multitechnique approach

Slota, Michael; Jiang, Shang‐Da; Heintze, Eric; Rechkemmer, Yvonne; Dressel, Martin; Slageren, Joris van; Bogani, Lapo

doi:10.1103/physrevb.99.134410

Cited by 8 publications

(6 citation statements)

References 65 publications

(74 reference statements)

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“…As an advanced functionality of NLO materials, optical-stimulation control of SHG is attractive. − To demonstrate such a functionality, a cyanide-bridged metal assembly is a useful system. Cyanide-bridged metal assemblies − exhibit various functionalities, including thermal phase transition, − photoinduced magnetization, ,− and gas-adsorption-induced magnetism. , As a building block of cyanide-bridged bimetal assemblies, cyanidometallates such as hexacyanidometallates ([M(CN) 6 ] n − ), heptacyanidometallates ([M(CN) 7 ] n − ), and octacyanidometallates ([M(CN) 8 ] n − ) are popular. Nitrosyl metal complexes (M–NO) are also attractive from the angle of functionality.…”

Section: Introductionmentioning

confidence: 99%

Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium–Iron Nitrosyl Metal Assembly

et al. 2021

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Nitrosyl metal complexes (M−NO), in which nitrosyl ligands are coordinated to transition-metal ions, have been studied from the viewpoints of physiological activity, catalytic activity, and photosensitivity. The structural flexibility and electric polarization of the nitrosyl ligand are attractive characteristics. Herein we show a photoswitchable nonlinear-optical (NLO) crystal based on a dysprosium−iron nitrosyl assembly. This crystal is composed of a one-dimensional chain structure in the polar Pna2 1 space group. Because of spontaneous electric polarization, it exhibits a NLO effect of second harmonic generation (SHG). The SHG signal reversibly changes by alternate irradiation with 473 and 804 nm laser lights. The observed photoreversible switching effect on SHG is caused by photoinduced linkage isomerization of the metal nitrosyl sites, i.e., MN + O ↔ MON + . Such an optically switchable NLO crystal should be useful for optical devices such as optical filters and optical shutters as well as probes in SHG microscopy.

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Section: Introductionmentioning

confidence: 99%

Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium–Iron Nitrosyl Metal Assembly

et al. 2021

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“…Far-IR magnetospectroscopy (FIRMS) has been utilized several times to measure energy levels in lanthanide complexes, and it provides a good measure of the magnetic anisotropy in the system. − Far-IR is useful for measuring magnetic transitions that are magnetic- and/or electric-dipole allowed. However, this method has rarely been used to study lanthanide-based SMMs, with most of the work performed by van Slageren et al − High-field, high-frequency electron paramagnetic resonance (HFEPR) has a typical upper frequency limit of ∼33 cm –1 , although a few cases exist where HFEPR has been pushed to up to 100 cm –1 . , Thus, HFEPR is often inadequate to study f-element complexes as they typically have energy levels above 100 cm –1 . Far-IR spectroscopy allows access to a higher-energy range and is therefore a more suitable method to directly determine the magnetic energy levels in transition metal and lanthanide complexes.…”

Section: Introductionmentioning

confidence: 99%

Inter-Kramers Transitions and Spin–Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

et al. 2020

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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 4 I 15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm–1, corresponding to transitions from the ground state, M J = ±15/2, to the first three excited states, M J = ±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.

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“…A thorough study on how to determine Combining Molecular Spintronics with Electron Paramagnetic… crystal-field parameters in a lanthanide compound using a plethora of spectroscopic techniques and magnometry techniques is demonstrated in Ref. [59].…”

Section: Theoretical Description Of Smmsmentioning

confidence: 99%

Combining Molecular Spintronics with Electron Paramagnetic Resonance: The Path Towards Single-Molecule Pulsed Spin Spectroscopy

Slota¹,

Bogani²

2020

Appl Magn Reson

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We provide a perspective on how single-molecule magnets can offer a platform to combine quantum transport and paramagnetic spectroscopy, so as to deliver time-resolved electron paramagnetic resonance at the single-molecule level. To this aim, we first review the main principles and recent developments of molecular spintronics, together with the possibilities and limitations offered by current approaches, where interactions between leads and single-molecule magnets are important. We then review progress on the electron quantum coherence on devices based on molecular magnets, and the pulse sequences and techniques necessary for their characterization, which might find implementation at the single-molecule level. Finally, we highlight how some of the concepts can also be implemented by including all elements into a single molecule and we propose an analogy between donor–acceptor triads, where a spin center is sandwiched between a donor and an acceptor, and quantum transport systems. We eventually discuss the possibility of probing spin coherence during or immediately after the passage of an electron transfer, based on examples of transient electron paramagnetic resonance spectroscopy on molecular materials.

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Accurate and unequivocal determination of the crystal-field parameters of lanthanide ions via a multitechnique approach

Cited by 8 publications

References 65 publications

Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium–Iron Nitrosyl Metal Assembly

Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium–Iron Nitrosyl Metal Assembly

Inter-Kramers Transitions and Spin–Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

Combining Molecular Spintronics with Electron Paramagnetic Resonance: The Path Towards Single-Molecule Pulsed Spin Spectroscopy

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