New field-induced single ion magnets based on prolate Er(<scp>iii</scp>) and Yb(<scp>iii</scp>) ions: tuning the energy barrierUeffby the choice of counterions within an N3-tridentate Schiff-base scaffold

Gorczyński, Adam; Marcinkowski, Dawid; Kubicki, Maciej; Löffler, Marta; Korabik, Maria; Karbowiak, Mirosław; Wiśniewski, Piotr; Rudowicz, Czesław; Patroniak, Violetta

doi:10.1039/c7qi00727b

Cited by 32 publications

(11 citation statements)

References 134 publications

(188 reference statements)

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“…Since their discovery, lanthanide-based single molecular magnets [ 1 , 2 , 3 ] have been the subject of great interest to researchers exploring the field of molecular magnetism. From a theoretical perspective, the quest for adequate methods and models to predict the magnetic behavior of these compounds has generated lively debates and a fruitful exchange of ideas in recent years [ 4 , 5 , 6 , 7 , 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

Georgiev

Chamati

2021

Molecules

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We study the magnetic properties of the erbium based compounds, Na9[Er(W5O18)2] and [(Pc)Er{Pc{N(C4H9)2}8}]·/−, in the framework of an effective spin exchange model involving delocalized electrons occupying molecular orbitals. The calculations successfully reproduce the experimental data available in the literature for the magnetic spectrum, magnetization and molar susceptibility in dc and ac fields. Owing to their similar molecular geometry, the compounds’ magnetic behaviors are interpreted in terms of the same set of active orbitals and thus the same effective spin coupling scheme. For all three complexes, the model predicts a prompt change in the ground state from a Kramer’s doublet at zero fields to a fully polarized quartet one brought about by the action of an external magnetic field without Zeeman splitting. This alteration is attributed to the enhancement of the effect of orbital interactions over the spin exchange as the magnitude of the external magnetic field increases.

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Section: Introductionmentioning

confidence: 99%

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

Georgiev

Chamati

2021

Molecules

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“…S1). [25][26][27][28][29][30][31][32] Our central hypothesis for the correlation between molecular structure and the ultra-narrow linewidth is that the rigidity of the ferrocene backbone in the supporting ligand sphere minimize inhomogeneous broadening and f/d orbital coupling, respectively. For example, Yb(trensal) (where H3(trensal) is 2,2',2"tris(salicylideneimino)triethylamine) is a compound with a high degree of magnetic anisotropy and well-defined optical features that shows a linewidth of 4.6 meV (fig.…”

Section: Resultsmentioning

confidence: 99%

Toward liquid cell quantum sensing: Ytterbium complexes with ultra-narrow absorption

Shin

Zhao

Shen

et al. 2022

Preprint

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In quantum technology (such as atomic vapor cells used in precision magnetometry), the energetic disorder induced by a fluctuating liquid environment acts in direct opposition to the precise control required for coherence-based sensing. Overcoming fluctuations requires a protected quantum subspace that only weakly interacts with the local environment. Herein, we report a ferrocene-supported ytterbium complex ((thiolfan)YbCl(THF), thiolfan = 1,1′-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene) that exhibits an extraordinarily narrow absorption linewidth in solution at room temperature with a full-width at half-maximum of 0.625 ± 0.006 meV. A detailed spectroscopic analysis allows us to assign all near infrared (NIR) transitions to atom-centered f-f transitions, protected from the solvent environment. A combination of density functional theory and multireference methods match experimental transition energies and oscillator strengths, illustrating the role of spin-orbit coupling and asymmetric ligand field in enhancing absorption and pointing toward molecular design principles that create well-protected yet observable electronic transitions in lanthanide complexes. Narrow linewidths allow for a demonstration of extremely low-field magnetic circular dichroism at room temperature, employed to sense and image magnetic fields, down to Earth scale. We term this system an ‘atom-like molecular sensor’ (ALMS), and propose approaches to improve its performance.

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“…However these have been mainly performed on Tb III and Dy III ions because of their efficient SMM behaviors coupled with good emission properties (see ref [54] for full review) [55][56][57][58][59]. The approach has been less developed on NIR emissive Ln-SMM where mainly Er III -SMM [60][61][62][63][64][65] and Yb III -SMM [29,[66][67][68][69][70][71][72][73] have been investigated. The drawback of these ions is that their emission is not always strong enough to allow for reliable magneto-luminescent correlations.…”

Section: Luminescence Measurementsmentioning

confidence: 99%

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

et al. 2018

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Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named NdMurex. Contrary to all known complexes of the 3d or 4f series, a dimeric compound was obtained. As for its already reported DyIII and YbIII parents, the NdIII complex responsible for the color-change behaves as a single-molecule magnet (SMM). This behavior was observed on both the crystalline (NdMurex: Ueff = 6.20(0.80) K, 4.31 cm−1; τ0 = 2.20(0.92) × 10−5 s, Hdc = 1200 Oe) and anhydrous form (NdMurexAnhy: Ueff = 6.25(0.90) K, 4.34 cm−1; τ0 = 4.85(0.40) × 10−5 s, Hdc = 1200 Oe). The SMM behavior is reported also for the anhydrous CeIII derivative (CeMurexAnhy: Ueff = 5.40(0.75) K, 3.75 cm−1; τ0 = 3.02(1.10) × 10−5 s, Hdc = 400 Oe). The Near-Infrared Emission NIR emission was observed for NdMurexAnhy and highlights its bifunctionality.

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New field-induced single ion magnets based on prolate Er(iii) and Yb(iii) ions: tuning the energy barrierU_effby the choice of counterions within an N₃-tridentate Schiff-base scaffold

Abstract: Counterions modulate the structure and magnetic properties of rarely observed high-coordinate SIM species.

Cited by 32 publications

References 134 publications

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

Toward liquid cell quantum sensing: Ytterbium complexes with ultra-narrow absorption

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

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New field-induced single ion magnets based on prolate Er(iii) and Yb(iii) ions: tuning the energy barrierUeffby the choice of counterions within an N3-tridentate Schiff-base scaffold

Abstract: Counterions modulate the structure and magnetic properties of rarely observed high-coordinate SIM species.

Cited by 32 publications

References 134 publications

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

Toward liquid cell quantum sensing: Ytterbium complexes with ultra-narrow absorption

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

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New field-induced single ion magnets based on prolate Er(iii) and Yb(iii) ions: tuning the energy barrierU_effby the choice of counterions within an N₃-tridentate Schiff-base scaffold