Field-Induced Single Molecule Magnets of Phosphine- and Arsine-Oxides

Overview

Journal Front Chem

Specialty Chemistry

Date 2018 Sep 28

PMID 30258840

Citations 2

Authors

Matilde Fondo

Julio Corredoira-Vazquez

Ana M Garcia-Deibe

Jesus Sanmartin-Matalobos

Juan Manuel Herrera

Enrique Colacio

Affiliations

Soon will be listed here.

Abstract

The coordination chemistry of dysprosium and terbium toward phosphine and arsine oxides was further explored. Thus, the new nitrate [M(NO)(PhPO)] ( = Tb, ; Dy, ), [Dy(NO)(EtOH)(PhXO)] ( = P, ; As, ), chloride [DyCl(PhAsO)]Cl (), triflate [Dy(OTf)(MePhPO)]OTf (; OTf = triflate) and hexafluoroacetylacetonate [M(hfa)(PhPO)] (hfa = hexafluoroacetylacetonate; = Tb, ; Dy, ) complexes were isolated and fully characterized. The crystal structures of ·CHCN, ·CHCN, , ·2.75EtOH·1.25HO, , , and show MO cores in , and , with highly distorted geometry, between spherical capped square antiprism and muffin-like, hexacoordinated environments for the dysprosium ions in and , with octahedral geometry, and octa-coordination for the lanthanoid metals in and , with geometry closer to square antiprism. Comparison of the magnetic behavior of all the complexes allows analyzing which metal ion (Tb or Dy), phosphine or arsine oxide, or anionic ligand favor more the slow relaxation of the magnetization. Alternating current magnetic measurements show that only , , and present slow relaxation of the magnetization in the presence of an external magnetic field, being the complex with the highest (44.85 K) of those described herein.

Citing Articles

Solid State and Solution Structures of Lanthanide Nitrate Complexes of Tris-(1-napthylphosphine oxide).

Coles S, McCormick McPherson L, Platt A, Singh K Molecules. 2024; 29(11).

PMID: 38893455 PMC: 11173986. DOI: 10.3390/molecules29112580.

Co(II) single-ion magnets: synthesis, structure, and magnetic properties.

Jurakova J, Salitros I Monatsh Chem. 2022; 153(11):1001-1036.

PMID: 35615113 PMC: 9123880. DOI: 10.1007/s00706-022-02920-0.

References

Ruiz-Martinez A, Casanova D, Alvarez S . Polyhedral structures with an odd number of vertices: nine-coordinate metal compounds. Chemistry. 2007; 14(4):1291-303. DOI: 10.1002/chem.200701137. View

Lu J, Guo M, Tang J . Recent Developments in Lanthanide Single-Molecule Magnets. Chem Asian J. 2017; 12(21):2772-2779. DOI: 10.1002/asia.201701032. 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

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

Ishikawa N, Sugita M, Wernsdorfer W . Quantum tunneling of magnetization in lanthanide single-molecule magnets: bis(phthalocyaninato)terbium and bis(phthalocyaninato)dysprosium anions. Angew Chem Int Ed Engl. 2005; 44(19):2931-5. DOI: 10.1002/anie.200462638. View

Sheldrick G . SHELXT - integrated space-group and crystal-structure determination. Acta Crystallogr A Found Adv. 2014; 71(Pt 1):3-8. PMC: 4283466. DOI: 10.1107/S2053273314026370. View

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

Sheldrick G . Crystal structure refinement with SHELXL. Acta Crystallogr C Struct Chem. 2015; 71(Pt 1):3-8. PMC: 4294323. DOI: 10.1107/S2053229614024218. View

10.

Ungur L, Chibotaru L . Magnetic anisotropy in the excited states of low symmetry lanthanide complexes. Phys Chem Chem Phys. 2011; 13(45):20086-90. DOI: 10.1039/c1cp22689d. View

11.

Chen Y, Liu J, Lan Y, Zhong Z, Mansikkamaki A, Ungur L . Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal Dy Single-Ion Magnet. Chemistry. 2017; 23(24):5708-5715. DOI: 10.1002/chem.201606029. View

12.

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

13.

Shiddiq M, Komijani D, Duan Y, Gaita-Arino A, Coronado E, Hill S . Enhancing coherence in molecular spin qubits via atomic clock transitions. Nature. 2016; 531(7594):348-51. DOI: 10.1038/nature16984. View

14.

Ding Y, Chilton N, Winpenny R, Zheng Y . On Approaching the Limit of Molecular Magnetic Anisotropy: A Near-Perfect Pentagonal Bipyramidal Dysprosium(III) Single-Molecule Magnet. Angew Chem Int Ed Engl. 2016; 55(52):16071-16074. DOI: 10.1002/anie.201609685. View

15.

Ruiz J, Mota A, Rodriguez-Dieguez A, Titos S, Herrera J, Ruiz E . Field and dilution effects on the slow relaxation of a luminescent DyO9 low-symmetry single-ion magnet. Chem Commun (Camb). 2012; 48(64):7916-8. DOI: 10.1039/c2cc32518g. View

16.

Blessing R . An empirical correction for absorption anisotropy. Acta Crystallogr A. 1995; 51 ( Pt 1):33-8. DOI: 10.1107/s0108767394005726. View

17.

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

18.

Sheldrick G . A short history of SHELX. Acta Crystallogr A. 2007; 64(Pt 1):112-22. DOI: 10.1107/S0108767307043930. View

19.

Bowden A, Horton P, Platt A . Lanthanide nitrate complexes of tri-isobutylphosphine oxide: solid state and CD2Cl2 solution structures. Inorg Chem. 2011; 50(6):2553-61. DOI: 10.1021/ic102385p. View