Opening magnetic hysteresis <i>via</i> improving the planarity of equatorial coordination by hydrogen bonding

Qu, Yun-Xia; Ruan, Ze‐Yu; Lyu, Bang-Heng; Chen, Yan‐Cong; Huang, Guo‐Zhang; Liu, Jun‐Liang; Tong, Ming‐Liang

doi:10.1039/d2dt01107g

Cited by 5 publications

(5 citation statements)

References 90 publications

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“…Both inphase and out-of-phase ac susceptibilities of 1Dy show a strong response to frequency (ν) and temperature (T) even under zero field below 19 K (Figure 5a S7). [23] The plot of lnτ vs. T À 1 is well fitted to the equation ( 1) containing QTM, Raman and Orbach processes, [24] giving parameters of U eff /k B = 277 K and τ 0 = 7.16 × 10 À 11 s, C = 1.17 × 10 À 3 K À 4.42 s À 1 , n = 4.42, τ QTM = 0.188 s (Table 2, Figure S22). Notably, this spin-reversal effective barrier is the highest among all light-responsive Ln-SMMs reported so far.…”

Section: Resultsmentioning

confidence: 93%

Photo‐responsive Single‐Molecule Magnet Showing 0D to 1D Single‐Crystal‐to‐Single‐Crystal Structural Transition and Hysteresis Modulation

Huang

Zheng

2023

Angewandte Chemie

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Photo‐responsive lanthanide‐based single‐molecule magnets (SMM) hold great promise for future switching and memory devices. Herein, we report a dysprosium phosphonate [DyIII(SCN)2(NO3)(depma)2(4‐hpy)2] (1Dy), which features a supramolecular framework containing layers of hydrogen‐bonding network and pillars of π–π interacted anthracene units. The photocycloaddition reaction of anthracene pairs led to a rapid and reversible single‐crystal‐to‐single‐crystal (SC–SC) structural transition to form the 1D coordination polymer [DyIII(SCN)2(NO3)(depma2)(4‐hpy)2]n (2Dy), accompanied by photoswitchable SMM properties with the reduction of effective energy barrier by half and the narrowing of the butterfly‐like hysteresis loop. The diluted sample showed a photo‐induced switch of the blocking temperature (TB) from 3.8 K for 1Dy@Y to 2.6 K for 2Dy@Y. This work may inspire the construction of lanthanide‐based molecular materials with targeted photo‐responsive magnetic properties.

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Section: Resultsmentioning

confidence: 93%

Photo‐responsive Single‐Molecule Magnet Showing 0D to 1D Single‐Crystal‐to‐Single‐Crystal Structural Transition and Hysteresis Modulation

Huang

Zheng

2023

Angewandte Chemie

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“…34 Although several Ln coordination polymers with SMM behavior have been reported before, [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] Ln coordination polymers with SMM behavior constructed from seven-coordinated Ln ions are still scarce. [53][54][55][56][57] Besides the SMM behavior, bright luminescence varying from visible to near-infrared regions can be found in Ln complexes. The introduction of optical properties into SMMs is valuable.…”

Section: Introductionmentioning

confidence: 99%

“…34 Although several Ln coordination polymers with SMM behavior have been reported before, 34–52 Ln coordination polymers with SMM behavior constructed from seven-coordinated Ln ions are still scarce. 53–57…”

Section: Introductionmentioning

confidence: 99%

Single molecule magnet features in luminescent lanthanide coordination polymers with heptacoordinate Dy/Yb(iii) ions as nodes

Dong¹,

Yu²,

Peng³

et al. 2023

Dalton Trans.

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“…In this regard, a CCDC search yielded [Dy(dppbO2)1.5(H2O)5]I3•(dppbO2)•H2O•EtOH (5a, dppbO2 = 1,4butylenebis(diphenylphosphine oxide)) and {[Dy(dppbO2)(H2O)5]I3•2(Ph3PO)•0.5H2O•0.5EtOH}n (5b) studied by Tong and co-workers. 77 Quite interestingly, moving from dinuclear (5a) to the 1D polymer (5b) leads to improving the equatorial planarity of the water molecules. As a result of this, an almost two times increase in the TB value is observed from 5a to 5b (FC/ZFC TB value is 4.5 K (9.3 K) for 5a(5b)), supporting our theoretical predictions.…”

Section: Role Of Out-of-plane Bending Of Water In Controlling the Uef...mentioning

confidence: 99%

Investigating the Interplay Between Spin-Vibrational Coupling and Blocking Temperature in Designing High-Performance Pseudo D5h Dy(III) Single Ion Magnets

Dey,

Sharma,

Rajaraman

2023

Preprint

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At the cutting edge of high-performance single-molecule magnets (SMMs) lie lanthanide-based complexes, renowned for their potent magnetic anisotropy. The performance of the SMMs is measured generally via the barrier height for magnetization reversal (Ueff) and blocking temperature (TB), below which the magnetization is fully frozen. To enhance the Ueff and TB values in lanthanide-based SMMs, the static crystal field splitting of mJ levels has been effectively adjusted through ligand design, leveraging the oblate/prolate ground state 4f electron density shape. However, the maximum fine-tuning that can be achieved via ligand design called the axial limit is already reached in this class of compounds and demand new design principle to enhance the SMM characteristics to suit end-user applications. Among other avenues that can be explored to improve the SMM characteristics, a deeper understanding of spin-phonon coupling, critical to advancing TB values, offers numerous advantages. However, there are only a handful of examples where this is deciphered. In this work, using a combination of DFT and ab initio CASSCF calculations, we have performed spin-phonon calculations of five classes of pseudo D5h Dy(III) SIMs exhibiting TB value in the range of 4.5 K to 36 K ([Dy(bbpen)Br] (1, H2bbpen=N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-methylpyridyl)ethylenediamine), [Dy(OCMe3)Br(THF)5][BPh4] (2) [Dy(OSiMe3)Br(THF)5] [BPh4] (3), [Dy(LN5)(Ph3SiO)2](BPh4).CH2Cl2 (4) and [L2Dy(H2O)5][I]3.L2.H2O (5, L = tBuPO(NHiPr)2)). The approach provided here not only reduces the computational cost but also suggests chemical intuition to improve the performance of this class of compounds. Our calculations reveal that low-energy vibrational modes govern the magnetization relaxation in these SIMs. A flexible first coordination sphere found on some of the complexes was found to be responsible for low-energy vibrations that flip the magnetization reducing the TB values drastically (complexes 2 and 3).On the other hand, a rigid first coordination sphere and a stiff ligand framework move the spin-vibrational coupling that causes the relaxation to lie beyond the secondary coordination sphere resulting in the increase of TB values. Learning from this exercise, we have undertaken several in silico models based on these vibrations to improvise the TB values. Some of these predictions were correlated to literature precedents, offering confidence in the methodology employed. To this end, our comprehensive investigation, involving twenty-three molecules/models and five sets of geometries for the pseudo D5h Dy(III) single-ion magnets (SIMs), unveils a treasure trove of chemically sound design clues, poised to enhance the TB values in this fascinating molecular realm.

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Opening magnetic hysteresis via improving the planarity of equatorial coordination by hydrogen bonding

Abstract: Through a mixed-ligand strategy, the structural change from a discrete dinuclear DyIII cluster to a one-dimensional polymeric chain was achieved, maintaining the two magnetic entities with the same {Dy(dppbO2)2(H2O)5} (dppbO2...

Cited by 5 publications

References 90 publications

Photo‐responsive Single‐Molecule Magnet Showing 0D to 1D Single‐Crystal‐to‐Single‐Crystal Structural Transition and Hysteresis Modulation

Photo‐responsive Single‐Molecule Magnet Showing 0D to 1D Single‐Crystal‐to‐Single‐Crystal Structural Transition and Hysteresis Modulation

Single molecule magnet features in luminescent lanthanide coordination polymers with heptacoordinate Dy/Yb(iii) ions as nodes

Investigating the Interplay Between Spin-Vibrational Coupling and Blocking Temperature in Designing High-Performance Pseudo D5h Dy(III) Single Ion Magnets

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