Alkali Metal Based Triimidosulfite Cages As Versatile Precursors for Single-Molecule Magnets

Overview

Journal Chemistry

Specialty Chemistry

Date 2022 Jan 18

PMID 35040528

Authors

Daniel Luert

Christina M Legendre

Regine Herbst-Irmer

Dietmar Stalke

Affiliations

Soon will be listed here.

Abstract

Based on the potassium [{S(tBuN) (tBuNH)} K (tmeda)-K {(HNtBu)(NtBu) S} ] (1) and sodium precursors [S(tBuN) (thf) -Na SNa (thf) (NtBu) S] (2), [S(tBuN) (thf) Na {(HNtBu)(NtBu) S}] (3) and [(tmeda) S-{Na (NtBu) S} ] (4) the syntheses and magnetic properties of three mixed metal triimidosulfite based alkali-lanthanide-metal-cages [(tBuNH)Dy{K(0.5tmeda)} {(NtBu) S} ] (5) and [ClLn{Na(thf)} {(NtBu) S} ] with Ln=Dy (6), Er (7) are reported. The corresponding potassium (1) and sodium (2-4) based cages are characterized through XRD and NMR experiments. Preventing lithium chloride co-complexation led to a significant increase of SMM performance to previously reported sulfur-nitrogen ligands. The subsequent Dy -complexes 5 and 6 display slow relaxation of magnetization at zero field, with relaxation barriers U=77.0 cm for 5, 512.9 and 316.3 cm for 6, respectively. Significantly, the latter complex 6 also exhibits a butterfly-shaped hysteresis up to 7 K.

Citing Articles

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single-Molecule Magnets.

Luert D, Legendre C, Herbst-Irmer R, Stalke D Chemistry. 2022; 28(15):e202104470.

PMID: 35040528 PMC: 9304269. DOI: 10.1002/chem.202104470.

References

Chilton N, Collison D, McInnes E, Winpenny R, Soncini A . An electrostatic model for the determination of magnetic anisotropy in dysprosium complexes. Nat Commun. 2013; 4:2551. DOI: 10.1038/ncomms3551. View

Pedersen K, Dreiser J, Weihe H, Sibille R, Johannesen H, Sorensen M . Design of Single-Molecule Magnets: Insufficiency of the Anisotropy Barrier as the Sole Criterion. Inorg Chem. 2015; 54(15):7600-6. DOI: 10.1021/acs.inorgchem.5b01209. View

Durrant J, Tang J, Mansikkamaki A, Layfield R . Enhanced single-molecule magnetism in dysprosium complexes of a pristine cyclobutadienyl ligand. Chem Commun (Camb). 2020; 56(34):4708-4711. DOI: 10.1039/d0cc01722a. View

Watt F, Krishna A, Golovanov G, Ott H, Schoch R, Wolper C . Monoanionic Anilidophosphine Ligand in Lanthanide Chemistry: Scope, Reactivity, and Electrochemistry. Inorg Chem. 2020; 59(5):2719-2732. DOI: 10.1021/acs.inorgchem.9b03071. View

Hubschle C, Sheldrick G, Dittrich B . ShelXle: a Qt graphical user interface for SHELXL. J Appl Crystallogr. 2012; 44(Pt 6):1281-1284. PMC: 3246833. DOI: 10.1107/S0021889811043202. View

Harriman K, Murugesu M . An Organolanthanide Building Block Approach to Single-Molecule Magnets. Acc Chem Res. 2016; 49(6):1158-67. DOI: 10.1021/acs.accounts.6b00100. View

Goodwin C, Ortu F, Reta D, Chilton N, Mills D . Molecular magnetic hysteresis at 60 kelvin in dysprosocenium. Nature. 2017; 548(7668):439-442. DOI: 10.1038/nature23447. View

Guo F, Day B, Chen Y, Tong M, Mansikkamaki A, Layfield R . Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet. Science. 2018; 362(6421):1400-1403. DOI: 10.1126/science.aav0652. View

Liddle S, van Slageren J . Improving f-element single molecule magnets. Chem Soc Rev. 2015; 44(19):6655-69. DOI: 10.1039/c5cs00222b. View

10.

Guo F, Day B, Chen Y, Tong M, Mansikkamaki A, Layfield R . A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit. Angew Chem Int Ed Engl. 2017; 56(38):11445-11449. DOI: 10.1002/anie.201705426. View

11.

Ako A, Hewitt I, Mereacre V, Clerac R, Wernsdorfer W, Anson C . A ferromagnetically coupled mn(19) aggregate with a record S=83/2 ground spin state. Angew Chem Int Ed Engl. 2006; 45(30):4926-9. DOI: 10.1002/anie.200601467. View

12.

Stalke D . Polyimido sulfur anions and ylides. Chem Commun (Camb). 2012; 48(77):9559-73. DOI: 10.1039/c2cc33221c. View

13.

Klementyeva S, Gritsan N, Khusniyarov M, Witt A, Dmitriev A, Suturina E . The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp* (RN=) S], Ln=Sm, Eu, Yb; R=SiMe. Chemistry. 2016; 23(6):1278-1290. DOI: 10.1002/chem.201604340. View

14.

Krause L, Herbst-Irmer R, Sheldrick G, Stalke D . Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination. J Appl Crystallogr. 2015; 48(Pt 1):3-10. PMC: 4453166. DOI: 10.1107/S1600576714022985. View

15.

Luert D, Legendre C, Herbst-Irmer R, Stalke D . Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single-Molecule Magnets. Chemistry. 2022; 28(15):e202104470. PMC: 9304269. DOI: 10.1002/chem.202104470. View

16.

Leuenberger M, Loss D . Quantum computing in molecular magnets. Nature. 2001; 410(6830):789-93. DOI: 10.1038/35071024. View

17.

Carl E, Demeshko S, Meyer F, Stalke D . Triimidosulfonates as Acute Bite-Angle Chelates: Slow Relaxation of the Magnetization in Zero Field and Hysteresis Loop of a Co(II) Complex. Chemistry. 2015; 21(28):10109-15. DOI: 10.1002/chem.201406083. View

18.

Raman K, Kamerbeek A, Mukherjee A, Atodiresei N, Sen T, Lazic P . Interface-engineered templates for molecular spin memory devices. Nature. 2013; 493(7433):509-13. DOI: 10.1038/nature11719. View

19.

Woodruff D, Winpenny R, Layfield R . Lanthanide single-molecule magnets. Chem Rev. 2013; 113(7):5110-48. DOI: 10.1021/cr400018q. View

20.

Jung J, Legendre C, Herbst-Irmer R, Stalke D . Exchange Coupling in Binuclear Manganese and Cobalt Complexes with the Tetraimido Sulfate Anion [S(NBu)]. Inorg Chem. 2020; 60(2):967-972. DOI: 10.1021/acs.inorgchem.0c03085. View