Influencing the Properties of Dysprosium Single-molecule Magnets with Phosphorus Donor Ligands

Overview

Journal Nat Commun

Specialty Biology

Date 2015 Jul 2

PMID 26130418

Citations 13

Authors

Thomas Pugh

Floriana Tuna

Liviu Ungur

David Collison

Eric J L McInnes

Liviu F Chibotaru

Richard A Layfield

Affiliations

Soon will be listed here.

Abstract

Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers' doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm(-1) and magnetic hysteresis up to 4.4 K.

Citing Articles

f-Element heavy pnictogen chemistry.

Du J, Cobb P, Ding J, Mills D, Liddle S Chem Sci. 2023; 15(1):13-45.

PMID: 38131077 PMC: 10732230. DOI: 10.1039/d3sc05056d.

Targeted Synthesis of End-On Dinitrogen-Bridged Lanthanide Metallocenes and Their Reactivity as Divalent Synthons.

Mondal A, Price C, Tang J, Layfield R J Am Chem Soc. 2023; 145(36):20121-20131.

PMID: 37656516 PMC: 10510326. DOI: 10.1021/jacs.3c07600.

Structural and Magnetization Dynamics of Borohydride-Bridged Rare-Earth Metallocenium Cations.

Price C, Mondal A, Durrant J, Tang J, Layfield R Inorg Chem. 2023; 62(25):9924-9933.

PMID: 37314885 PMC: 10302870. DOI: 10.1021/acs.inorgchem.3c01038.

Experimental and theoretical interpretation of the magnetic behavior of two Dy(iii) single-ion magnets constructed through β-diketonate ligands with different substituent groups (-Cl/-OCH).

Zhang S, Mo W, Zhang J, Wu H, Li M, Lu X RSC Adv. 2022; 8(52):29513-29525.

PMID: 35557993 PMC: 9092431. DOI: 10.1039/c8ra06240d.

Cadmium-Inspired Self-Polymerization of {LnCd} Units: Structure, Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm, Eu, Tb, Dy, Ho, Er, Yb).

Shmelev M, Polunin R, Gogoleva N, Evstifeev I, Vasilyev P, Dmitriev A Molecules. 2021; 26(14).

PMID: 34299571 PMC: 8307922. DOI: 10.3390/molecules26144296.

References

Thiele S, Balestro F, Ballou R, Klyatskaya S, Ruben M, Wernsdorfer W . Electrically driven nuclear spin resonance in single-molecule magnets. Science. 2014; 344(6188):1135-8. DOI: 10.1126/science.1249802. View

Chibotaru L, Ungur L . Ab initio calculation of anisotropic magnetic properties of complexes. I. Unique definition of pseudospin Hamiltonians and their derivation. J Chem Phys. 2012; 137(6):064112. DOI: 10.1063/1.4739763. View

Perfetti M, Cucinotta G, Boulon M, El Hallak F, Gao S, Sessoli R . Angular-resolved magnetometry beyond triclinic crystals part II: torque magnetometry of Cp*ErCOT single-molecule magnets. Chemistry. 2014; 20(43):14051-6. DOI: 10.1002/chem.201404218. View

Layfield R, McDouall J, Sulway S, Tuna F, Collison D, Winpenny R . Influence of the N-bridging ligand on magnetic relaxation in an organometallic dysprosium single-molecule magnet. Chemistry. 2010; 16(15):4442-6. DOI: 10.1002/chem.201000158. View

Wicker B, Scott J, Andino J, Gao X, Park H, Pink M . Phosphinidene complexes of scandium: powerful PAr group-transfer vehicles to organic and inorganic substrates. J Am Chem Soc. 2010; 132(11):3691-3. DOI: 10.1021/ja100214e. View

Ganivet C, Ballesteros B, de la Torre G, Clemente-Juan J, Coronado E, Torres T . Influence of peripheral substitution on the magnetic behavior of single-ion magnets based on homo- and heteroleptic Tb(III) bis(phthalocyaninate). Chemistry. 2012; 19(4):1457-65. DOI: 10.1002/chem.201202600. View

Tuna F, Smith C, Bodensteiner M, Ungur L, Chibotaru L, McInnes E . A high anisotropy barrier in a sulfur-bridged organodysprosium single-molecule magnet. Angew Chem Int Ed Engl. 2012; 51(28):6976-80. DOI: 10.1002/anie.201202497. View

Blagg R, Ungur L, Tuna F, Speak J, Comar P, Collison D . Magnetic relaxation pathways in lanthanide single-molecule magnets. Nat Chem. 2013; 5(8):673-8. DOI: 10.1038/nchem.1707. View

Cui P, Chen Y, Xu X, Sun J . An unprecedented lanthanide phosphinidene halide: synthesis, structure and reactivity. Chem Commun (Camb). 2008; (43):5547-9. DOI: 10.1039/b813075b. View

10.

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

11.

Wang K, Luo G, Hong J, Zhou X, Weng L, Luo Y . Homometallic rare-Earth metal phosphinidene clusters: synthesis and reactivity. Angew Chem Int Ed Engl. 2013; 53(4):1053-6. DOI: 10.1002/anie.201307422. View

12.

Vincent R, Klyatskaya S, Ruben M, Wernsdorfer W, Balestro F . Electronic read-out of a single nuclear spin using a molecular spin transistor. Nature. 2012; 488(7411):357-60. DOI: 10.1038/nature11341. View

13.

Cornia A, Mannini M, Sainctavit P, Sessoli R . Chemical strategies and characterization tools for the organization of single molecule magnets on surfaces. Chem Soc Rev. 2011; 40(6):3076-91. DOI: 10.1039/c0cs00187b. View

14.

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

15.

Ungur L, Le Roy J, Korobkov I, Murugesu M, Chibotaru L . Fine-tuning the local symmetry to attain record blocking temperature and magnetic remanence in a single-ion magnet. Angew Chem Int Ed Engl. 2014; 53(17):4413-7. DOI: 10.1002/anie.201310451. View

16.

Moreno Pineda E, Chilton N, Marx R, Dorfel M, Sells D, Neugebauer P . Direct measurement of dysprosium(III)···dysprosium(III) interactions in a single-molecule magnet. Nat Commun. 2014; 5:5243. DOI: 10.1038/ncomms6243. View

17.

Lodi Rizzini A, Krull C, Balashov T, Mugarza A, Nistor C, Yakhou F . Exchange biasing single molecule magnets: coupling of TbPc2 to antiferromagnetic layers. Nano Lett. 2012; 12(11):5703-7. DOI: 10.1021/nl302918d. View

18.

AlDamen M, Cardona-Serra S, Clemente-Juan J, Coronado E, Gaita-Arino A, Marti-Gastaldo C . Mononuclear lanthanide single molecule magnets based on the polyoxometalates [Ln(W5O18)2]9- and [Ln(beta2-SiW11O39)2]13- (Ln(III) = Tb, Dy, Ho, Er, Tm, and Yb). Inorg Chem. 2009; 48(8):3467-79. DOI: 10.1021/ic801630z. View

19.

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

20.

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