Syntheses, Structures, and Magnetic Properties of Acetate-bridged Lanthanide Complexes Based on a Tripodal Oxygen Ligand

Overview

Journal Front Chem

Specialty Chemistry

Date 2022 Oct 6

PMID 36199666

Authors

Yu Sheng

Yu-Jing Jiang

Zi-Hang Cheng

Ru-Chan Liu

Jing-Yuan Ge

Feng Gao

Affiliations

Soon will be listed here.

Abstract

Four homodinuclear lanthanide complexes, Dy (L)(OAc) (), Tb (L)(OAc) (), Ho(L)(OAc) (), and Gd (L)(OAc) (), have been synthesized and characterized based on a tripodal oxygen ligand Na [(η-CH)Co(P(O)(OCH))] (NaL). Structural analyses show that the acetate anions bridge two symmetry-related Ln ions in the μ:η:η and μ:η:η coordination patterns, and each lanthanide (III) ion owns a twisted square antiprism (SAPR) conformation. Static magnetic measurements reveal the weak intramolecular ferromagnetic interaction between dysprosium (III) ions in and antiferromagnetic Ln···Ln couplings in the other three complexes. Through the analysis of the ligand-field effect and magnetic anisotropy axis orientation, the reasons for the lack of dynamic magnetic behavior in were identified.

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

Chilton N, Anderson R, Turner L, Soncini A, Murray K . PHI: a powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d- and f-block complexes. J Comput Chem. 2013; 34(13):1164-75. DOI: 10.1002/jcc.23234. View

Lim K, Baldovi J, Lee W, Song J, Yoon S, Suh B . Switching of Slow Magnetic Relaxation Dynamics in Mononuclear Dysprosium(III) Compounds with Charge Density. Inorg Chem. 2016; 55(11):5398-404. DOI: 10.1021/acs.inorgchem.6b00410. View

Bala S, Huang G, Ruan Z, Wu S, Liu Y, Wang L . A square antiprism dysprosium single-ion magnet with an energy barrier over 900 K. Chem Commun (Camb). 2019; 55(67):9939-9942. DOI: 10.1039/c9cc05135j. View

Hutchings A, Habib F, Holmberg R, Korobkov I, Murugesu M . Structural rearrangement through lanthanide contraction in dinuclear complexes. Inorg Chem. 2014; 53(4):2102-12. DOI: 10.1021/ic402682r. View

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

Li X, Liu Y, Zhu G, Yang F, Gao F . Successive syntheses and magnetic properties of homodinuclear lanthanide macrocyclic complexes. Dalton Trans. 2021; 50(35):12215-12225. DOI: 10.1039/d1dt01514a. View

Ishikawa N, Sugita M, Ishikawa T, Koshihara S, Kaizu Y . Lanthanide double-decker complexes functioning as magnets at the single-molecular level. J Am Chem Soc. 2003; 125(29):8694-5. DOI: 10.1021/ja029629n. View

Thomas-Hargreaves L, Hunger D, Kern M, Wooles A, van Slageren J, Chilton N . Insights into @metal-symmetry single-molecule magnetism: the case of a dysprosium-bis(boryloxide) complex. Chem Commun (Camb). 2020; 57(6):733-736. DOI: 10.1039/d0cc07446b. View

10.

Bogani L, Wernsdorfer W . Molecular spintronics using single-molecule magnets. Nat Mater. 2008; 7(3):179-86. DOI: 10.1038/nmat2133. View

11.

Chen Y, Liu J, Ungur L, Liu J, Li Q, Wang L . Symmetry-Supported Magnetic Blocking at 20 K in Pentagonal Bipyramidal Dy(III) Single-Ion Magnets. J Am Chem Soc. 2016; 138(8):2829-37. DOI: 10.1021/jacs.5b13584. View

12.

Van Raden J, Alexandropoulos D, Slota M, Sopp S, Matsuno T, Thompson A . Singly and Triply Linked Magnetic Porphyrin Lanthanide Arrays. J Am Chem Soc. 2022; 144(19):8693-8706. PMC: 9121389. DOI: 10.1021/jacs.2c02084. View

13.

Gao F, Cui L, Song Y, Li Y, Zuo J . Calix[4]arene-supported mononuclear lanthanide single-molecule magnet. Inorg Chem. 2013; 53(1):562-7. DOI: 10.1021/ic4026624. View

14.

Parmar V, Mills D, Winpenny R . Mononuclear Dysprosium Alkoxide and Aryloxide Single-Molecule Magnets. Chemistry. 2021; 27(28):7625-7645. PMC: 8252031. DOI: 10.1002/chem.202100085. View

15.

Liu J, Chen Y, Liu J, Vieru V, Ungur L, Jia J . A Stable Pentagonal Bipyramidal Dy(III) Single-Ion Magnet with a Record Magnetization Reversal Barrier over 1000 K. J Am Chem Soc. 2016; 138(16):5441-50. DOI: 10.1021/jacs.6b02638. View

16.

Ding X, Zhai Y, Han T, Chen W, Ding Y, Zheng Y . A Local D Symmetric Dysprosium(III) Single-Molecule Magnet with an Energy Barrier Exceeding 2000 K*. Chemistry. 2020; 27(8):2623-2627. DOI: 10.1002/chem.202003931. View

17.

Shen F, Pramanik K, Brandao P, Zhang Y, Jana N, Wang X . Macrocycle supported dimetallic lanthanide complexes with slow magnetic relaxation in Dy analogues. Dalton Trans. 2020; 49(40):14169-14179. DOI: 10.1039/d0dt02778b. View

18.

Morita T, Damjanovic M, Katoh K, Kitagawa Y, Yasuda N, Lan Y . Comparison of the Magnetic Anisotropy and Spin Relaxation Phenomenon of Dinuclear Terbium(III) Phthalocyaninato Single-Molecule Magnets Using the Geometric Spin Arrangement. J Am Chem Soc. 2018; 140(8):2995-3007. DOI: 10.1021/jacs.7b12667. View

19.

Zhu Z, Zhao C, Feng T, Liu X, Ying X, Li X . Air-Stable Chiral Single-Molecule Magnets with Record Anisotropy Barrier Exceeding 1800 K. J Am Chem Soc. 2021; 143(27):10077-10082. DOI: 10.1021/jacs.1c05279. View

20.

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