Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes

Nicholas F Chilton; Glen B Deacon; Olga Gazukin; Peter C Junk; Berthold Kersting; Stuart K Langley; Boujemaa Moubaraki; Keith S Murray; Frederik Schleife; Mahasish Shome; David R Turner; Julia A Walker

doi:10.1021/ic402672m

Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes

Nicholas F Chilton, Glen B Deacon, Olga Gazukin, Peter C Junk, Berthold Kersting, Stuart K Langley, Boujemaa Moubaraki, Keith S Murray, Frederik Schleife, Mahasish Shome, David R Turner, Julia A Walker

Research output: Contribution to journal › Article › peer-review

Abstract

Three complexes of the form [LnIII3(OQ)9] (Ln = Gd, Tb, Dy; OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = ?0.068(2) cm?1. The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.

Original language	English
Pages (from-to)	2528-2534
Number of pages	7
Journal	Inorganic Chemistry: including bioinorganic chemistry
Volume	53
Issue number	5
DOIs	https://doi.org/10.1021/ic402672m
Publication status	Published - Feb 2014

Access to Document

10.1021/ic402672m

http://dx.doi.org/10.1021/ic402672m

CCDC 966476: Experimental Crystal Structure Determination
Chilton, N. (Contributor), Deacon, G. B. (Contributor), Gazukin, O. (Contributor), Junk, P. C. (Contributor), Kersting, B. (Contributor), Langley, S. K. (Contributor), Moubaraki, B. (Contributor), Murray, K. S. (Contributor), Schleife, F. (Contributor), Shome, M. (Contributor), Turner, D. R. (Contributor) & Walker, J. A. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc11fpnt, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc11fpnt&sid=DataCite
Dataset

Cite this

Chilton, N. F., Deacon, G. B., Gazukin, O., Junk, P. C., Kersting, B., Langley, S. K., Moubaraki, B., Murray, K. S., Schleife, F., Shome, M., Turner, D. R., & Walker, J. A. (2014). Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes. Inorganic Chemistry: including bioinorganic chemistry , 53(5), 2528-2534. https://doi.org/10.1021/ic402672m

@article{4d8dfa2a0b8b4719b2f679883321c306,

title = "Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes",

abstract = "Three complexes of the form [LnIII3(OQ)9] (Ln = Gd, Tb, Dy; OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = ?0.068(2) cm?1. The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.",

author = "Chilton, {Nicholas F} and Deacon, {Glen B} and Olga Gazukin and Junk, {Peter C} and Berthold Kersting and Langley, {Stuart K} and Boujemaa Moubaraki and Murray, {Keith S} and Frederik Schleife and Mahasish Shome and Turner, {David R} and Walker, {Julia A}",

year = "2014",

month = feb,

doi = "10.1021/ic402672m",

language = "English",

volume = "53",

pages = "2528--2534",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

Chilton, NF, Deacon, GB, Gazukin, O, Junk, PC, Kersting, B, Langley, SK, Moubaraki, B, Murray, KS, Schleife, F, Shome, M, Turner, DR & Walker, JA 2014, 'Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes', Inorganic Chemistry: including bioinorganic chemistry , vol. 53, no. 5, pp. 2528-2534. https://doi.org/10.1021/ic402672m

TY - JOUR

T1 - Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes

AU - Chilton, Nicholas F

AU - Deacon, Glen B

AU - Gazukin, Olga

AU - Junk, Peter C

AU - Kersting, Berthold

AU - Langley, Stuart K

AU - Moubaraki, Boujemaa

AU - Murray, Keith S

AU - Schleife, Frederik

AU - Shome, Mahasish

AU - Turner, David R

AU - Walker, Julia A

PY - 2014/2

Y1 - 2014/2

N2 - Three complexes of the form [LnIII3(OQ)9] (Ln = Gd, Tb, Dy; OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = ?0.068(2) cm?1. The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.

AB - Three complexes of the form [LnIII3(OQ)9] (Ln = Gd, Tb, Dy; OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = ?0.068(2) cm?1. The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.

U2 - 10.1021/ic402672m

DO - 10.1021/ic402672m

M3 - Article

VL - 53

SP - 2528

EP - 2534

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -

Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes

Abstract

Access to Document

Fingerprint

Datasets

CCDC 966476: Experimental Crystal Structure Determination

Cite this