Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift

Elizaveta A. Suturina; Kevin Mason; Carlos F.G.C. Geraldes; Ilya Kuprov; David Parker

doi:10.1002/anie.201706931

Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift

Elizaveta A. Suturina, Kevin Mason, Carlos F.G.C. Geraldes, Ilya Kuprov, David Parker

Department of Chemistry

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

48 Citations (SciVal)

Abstract

A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory—that thermal energy is larger than the ligand field splitting—does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.

Original language	English
Pages (from-to)	12215-12218
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	40
Early online date	24 Aug 2017
DOIs	https://doi.org/10.1002/anie.201706931
Publication status	Published - 20 Sept 2017

Funding

We thank EPSRC for support (EP/N006909/1; EP/L01212X/ 1; EP/N006895/1). The authors acknowledge the use of the IRIDIS High Performance Computing Facility, and associated services at the University of Southampton. C.F.G.C.G. was supported by a European Union COFUND/Durham University Senior Research Fellowship under EU grant agreement number 609412, hosted by Trevelyan College and Department of Chemistry. Preliminary work on the combinatorial fitting procedure by Steven G. Worswick is also gratefully acknowledged.

Keywords

lanthanides
ligand field
paramagnetic NMR
PARASHIFT
pseudocontact shift

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201706931

https://eprints.soton.ac.uk/414917/

Cite this

@article{519e2511996b4fb3bcfb664650e064fa,

title = "Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift",

abstract = "A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory—that thermal energy is larger than the ligand field splitting—does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.",

keywords = "lanthanides, ligand field, paramagnetic NMR, PARASHIFT, pseudocontact shift",

author = "Suturina, {Elizaveta A.} and Kevin Mason and Geraldes, {Carlos F.G.C.} and Ilya Kuprov and David Parker",

year = "2017",

month = sep,

day = "20",

doi = "10.1002/anie.201706931",

language = "English",

volume = "56",

pages = "12215--12218",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Inc.",

number = "40",

}

TY - JOUR

T1 - Beyond Bleaney's Theory

T2 - Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift

AU - Suturina, Elizaveta A.

AU - Mason, Kevin

AU - Geraldes, Carlos F.G.C.

AU - Kuprov, Ilya

AU - Parker, David

PY - 2017/9/20

Y1 - 2017/9/20

N2 - A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory—that thermal energy is larger than the ligand field splitting—does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.

AB - A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory—that thermal energy is larger than the ligand field splitting—does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.

KW - lanthanides

KW - ligand field

KW - paramagnetic NMR

KW - PARASHIFT

KW - pseudocontact shift

UR - http://www.scopus.com/inward/record.url?scp=85028022321&partnerID=8YFLogxK

U2 - 10.1002/anie.201706931

DO - 10.1002/anie.201706931

M3 - Article

AN - SCOPUS:85028022321

SN - 1433-7851

VL - 56

SP - 12215

EP - 12218

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 40

ER -

Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Elizaveta Suturina

High Performance Computing (HPC) Facility

Cite this

Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Profiles

Elizaveta Suturina

Equipment

High Performance Computing (HPC) Facility

Cite this