Slow Magnetic Relaxation in Octahedral Low-spin Ni(iii) Complexes

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Oct 13

PMID 30310588

Citations 3

Authors

Indrani Bhowmick

Andrew J Roehl

James R Neilson

Anthony K Rappe

Matthew P Shores

Affiliations

Soon will be listed here.

Abstract

Herein we report the first examples of single-molecule magnet (SMM) behaviour in = 1/2 Ni(iii) complexes. We find that low-spin 3d -[Ni(cyclam)(X)]Y complexes (cyclam = 1,4,8,11-tetraazacyclotetradecane; X and Y are singly charged anions) exhibit field-induced slow relaxation of magnetization for O-donor axial ligands (nitrate) but not for N-donor variants (isothiocyanate). Experimental and electronic structure computational investigations indicate that intrinsic spin polarisation of low-spin Ni(iii) is modulated significantly by local coordination geometry and supramolecular interactions. Solid state dilution of Ni(iii) with diamagnetic Co(iii) ions forms a related complex salt, [Ni Co (cyclam)(NO)](NO)·2HNO (0.1 < < 1), which preserves slow magnetic dynamics, thus supporting a molecular component to slow relaxation. An initial analysis of magnetic relaxation lifetime fits best to a combination of Raman and direct relaxation processes.

Citing Articles

Nickel Perfluoroalkyl Complexes Supported by Simple Acetate Coligands.

Ravidas C, Shreiber S, Kletsch L, Klein A, Vicic D Organometallics. 2024; 43(6):706-712.

PMID: 38550879 PMC: 10966735. DOI: 10.1021/acs.organomet.4c00029.

Slowing magnetic relaxation with open-shell diluents.

Moseley I, Ard C, DiVerdi J, Ozarowski A, Chen H, Zadrozny J Cell Rep Phys Sci. 2022; 3(3).

PMID: 35425929 PMC: 9007552. DOI: 10.1016/j.xcrp.2022.100802.

Magnetization Dynamics and Coherent Spin Manipulation of a Propeller Gd(III) Complex with the Smallest Helicene Ligand.

Handzlik G, Magott M, Arczynski M, Sheveleva A, Tuna F, Sarewicz M J Phys Chem Lett. 2020; 11(4):1508-1515.

PMID: 31994400 PMC: 7497647. DOI: 10.1021/acs.jpclett.9b03275.

References

Hino S, Maeda M, Yamashita K, Kataoka Y, Nakano M, Yamamura T . Linear trinuclear Zn(II)-Ce(III)-Zn(II) complex which behaves as a single-molecule magnet. Dalton Trans. 2013; 42(8):2683-6. DOI: 10.1039/c2dt32812g. View

Lopez N, Prosvirin A, Zhao H, Wernsdorfer W, Dunbar K . Heterospin single-molecule magnets based on terbium ions and TCNQF(4) radicals: interplay between single-molecule magnet and phonon bottleneck phenomena investigated by dilution studies. Chemistry. 2009; 15(42):11390-400. DOI: 10.1002/chem.200900629. View

Aromi G, Aguila D, Gamez P, Luis F, Roubeau O . Design of magnetic coordination complexes for quantum computing. Chem Soc Rev. 2011; 41(2):537-46. DOI: 10.1039/c1cs15115k. View

Chiorescu I , Wernsdorfer , Muller , Bogge , Barbara . Butterfly hysteresis loop and dissipative spin reversal in the S = 1/2, V15 molecular complex. Phys Rev Lett. 2000; 84(15):3454-7. DOI: 10.1103/PhysRevLett.84.3454. View

Ding M, Cutsail 3rd G, Aravena D, Amoza M, Rouzieres M, Dechambenoit P . A Low Spin Manganese(IV) Nitride Single Molecule Magnet. Chem Sci. 2016; 7(9):6132-6140. PMC: 5058364. DOI: 10.1039/C6SC01469K. View

Boca R, Rajnak C, Titis J, Valigura D . Field Supported Slow Magnetic Relaxation in a Mononuclear Cu(II) Complex. Inorg Chem. 2017; 56(3):1478-1482. DOI: 10.1021/acs.inorgchem.6b02535. View

Escalera-Moreno L, Baldovi J, Gaita-Arino A, Coronado E . Spin states, vibrations and spin relaxation in molecular nanomagnets and spin qubits: a critical perspective. Chem Sci. 2018; 9(13):3265-3275. PMC: 5935026. DOI: 10.1039/c7sc05464e. View

Mannini M, Pineider F, Sainctavit P, Danieli C, Otero E, Sciancalepore C . Magnetic memory of a single-molecule quantum magnet wired to a gold surface. Nat Mater. 2009; 8(3):194-7. DOI: 10.1038/nmat2374. View

Zheng Y, Evangelisti M, Tuna F, Winpenny R . Co-Ln mixed-metal phosphonate grids and cages as molecular magnetic refrigerants. J Am Chem Soc. 2011; 134(2):1057-65. DOI: 10.1021/ja208367k. View

10.

Harmer J, Finazzo C, Piskorski R, Bauer C, Jaun B, Duin E . Spin density and coenzyme M coordination geometry of the ox1 form of methyl-coenzyme M reductase: a pulse EPR study. J Am Chem Soc. 2005; 127(50):17744-55. DOI: 10.1021/ja053794w. View

11.

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

12.

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

13.

Lunghi A, Totti F, Sessoli R, Sanvito S . The role of anharmonic phonons in under-barrier spin relaxation of single molecule magnets. Nat Commun. 2017; 8:14620. PMC: 5343443. DOI: 10.1038/ncomms14620. View

14.

Lunghi A, Totti F, Sanvito S, Sessoli R . Intra-molecular origin of the spin-phonon coupling in slow-relaxing molecular magnets. Chem Sci. 2017; 8(9):6051-6059. PMC: 5625570. DOI: 10.1039/c7sc02832f. View

15.

Dunbar K . Editorial for the virtual issue on quantum molecular magnets. Inorg Chem. 2014; 51(22):12055-8. DOI: 10.1021/ic302312m. View

16.

Peng J, Zhang Q, Kong X, Zheng Y, Ren Y, Long L . High-nuclearity 3d-4f clusters as enhanced magnetic coolers and molecular magnets. J Am Chem Soc. 2012; 134(7):3314-7. DOI: 10.1021/ja209752z. View

17.

Singh S, Gupta T, Ungur L, Rajaraman G . Magnetic Relaxation in Single-Electron Single-Ion Cerium(III) Magnets: Insights from Ab Initio Calculations. Chemistry. 2015; 21(39):13812-9. DOI: 10.1002/chem.201501330. View

18.

Escalera-Moreno L, Suaud N, Gaita-Arino A, Coronado E . Determining Key Local Vibrations in the Relaxation of Molecular Spin Qubits and Single-Molecule Magnets. J Phys Chem Lett. 2017; 8(7):1695-1700. DOI: 10.1021/acs.jpclett.7b00479. View

19.

Tesi L, Lucaccini E, Cimatti I, Perfetti M, Mannini M, Atzori M . Quantum coherence in a processable vanadyl complex: new tools for the search of molecular spin qubits. Chem Sci. 2018; 7(3):2074-2083. PMC: 5968563. DOI: 10.1039/c5sc04295j. View

20.

Gomez-Coca S, Cremades E, Aliaga-Alcalde N, Ruiz E . Mononuclear single-molecule magnets: tailoring the magnetic anisotropy of first-row transition-metal complexes. J Am Chem Soc. 2013; 135(18):7010-8. DOI: 10.1021/ja4015138. View