Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes

Elizaveta A Suturina, Kevin Mason, Mauro Botta, Fabio Carniato, Ilya Kuprov, Nicholas F Chilton, Eric J L McInnes, Michele Vonci, David Parker

Research output: Contribution to journalArticle

Abstract

In three structurally related series of nine-coordinate lanthanide(iii) complexes (Ln = Tb, Dy, Ho, Er, Tm and Yb) based on triazacyclononane, solution NMR studies and DFT/CASSCF calculations have provided key information on the magnetic susceptibility anisotropy. Both experimental and computational approaches have revealed a poor correlation to Bleaney's theory of magnetic anisotropy. CASSCF calculations suggested that the magnetic susceptibility is very sensitive to small geometric variations within the first coordination sphere, whereas DFT analyses indicate that it is the thermal accessibility of low energy vibrational modes that may lead to distortion. Parallel NMRD and EPR studies on the three Gd(iii) complexes revealed good correspondence in estimating the electronic relaxation time. The Gd(iii) tris-pyridinecarboxylate complex possesses a very long electronic relaxation time making it a promising starting point for responsive gadolinium EPR probe design.

Original languageEnglish
Pages (from-to)8400-8409
Number of pages10
JournalDalton Transactions
Volume48
Issue number23
Early online date15 May 2019
DOIs
Publication statusPublished - 21 Jun 2019

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes. / Suturina, Elizaveta A; Mason, Kevin; Botta, Mauro; Carniato, Fabio; Kuprov, Ilya; Chilton, Nicholas F; McInnes, Eric J L; Vonci, Michele; Parker, David.

In: Dalton Transactions , Vol. 48, No. 23, 21.06.2019, p. 8400-8409.

Research output: Contribution to journalArticle

Suturina, EA, Mason, K, Botta, M, Carniato, F, Kuprov, I, Chilton, NF, McInnes, EJL, Vonci, M & Parker, D 2019, 'Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes', Dalton Transactions , vol. 48, no. 23, pp. 8400-8409. https://doi.org/10.1039/c9dt01069f
Suturina, Elizaveta A ; Mason, Kevin ; Botta, Mauro ; Carniato, Fabio ; Kuprov, Ilya ; Chilton, Nicholas F ; McInnes, Eric J L ; Vonci, Michele ; Parker, David. / Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes. In: Dalton Transactions . 2019 ; Vol. 48, No. 23. pp. 8400-8409.
@article{62de6b3450244171871981b29cf32def,
title = "Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes",
abstract = "In three structurally related series of nine-coordinate lanthanide(iii) complexes (Ln = Tb, Dy, Ho, Er, Tm and Yb) based on triazacyclononane, solution NMR studies and DFT/CASSCF calculations have provided key information on the magnetic susceptibility anisotropy. Both experimental and computational approaches have revealed a poor correlation to Bleaney's theory of magnetic anisotropy. CASSCF calculations suggested that the magnetic susceptibility is very sensitive to small geometric variations within the first coordination sphere, whereas DFT analyses indicate that it is the thermal accessibility of low energy vibrational modes that may lead to distortion. Parallel NMRD and EPR studies on the three Gd(iii) complexes revealed good correspondence in estimating the electronic relaxation time. The Gd(iii) tris-pyridinecarboxylate complex possesses a very long electronic relaxation time making it a promising starting point for responsive gadolinium EPR probe design.",
author = "Suturina, {Elizaveta A} and Kevin Mason and Mauro Botta and Fabio Carniato and Ilya Kuprov and Chilton, {Nicholas F} and McInnes, {Eric J L} and Michele Vonci and David Parker",
year = "2019",
month = "6",
day = "21",
doi = "10.1039/c9dt01069f",
language = "English",
volume = "48",
pages = "8400--8409",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "23",

}

TY - JOUR

T1 - Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes

AU - Suturina, Elizaveta A

AU - Mason, Kevin

AU - Botta, Mauro

AU - Carniato, Fabio

AU - Kuprov, Ilya

AU - Chilton, Nicholas F

AU - McInnes, Eric J L

AU - Vonci, Michele

AU - Parker, David

PY - 2019/6/21

Y1 - 2019/6/21

N2 - In three structurally related series of nine-coordinate lanthanide(iii) complexes (Ln = Tb, Dy, Ho, Er, Tm and Yb) based on triazacyclononane, solution NMR studies and DFT/CASSCF calculations have provided key information on the magnetic susceptibility anisotropy. Both experimental and computational approaches have revealed a poor correlation to Bleaney's theory of magnetic anisotropy. CASSCF calculations suggested that the magnetic susceptibility is very sensitive to small geometric variations within the first coordination sphere, whereas DFT analyses indicate that it is the thermal accessibility of low energy vibrational modes that may lead to distortion. Parallel NMRD and EPR studies on the three Gd(iii) complexes revealed good correspondence in estimating the electronic relaxation time. The Gd(iii) tris-pyridinecarboxylate complex possesses a very long electronic relaxation time making it a promising starting point for responsive gadolinium EPR probe design.

AB - In three structurally related series of nine-coordinate lanthanide(iii) complexes (Ln = Tb, Dy, Ho, Er, Tm and Yb) based on triazacyclononane, solution NMR studies and DFT/CASSCF calculations have provided key information on the magnetic susceptibility anisotropy. Both experimental and computational approaches have revealed a poor correlation to Bleaney's theory of magnetic anisotropy. CASSCF calculations suggested that the magnetic susceptibility is very sensitive to small geometric variations within the first coordination sphere, whereas DFT analyses indicate that it is the thermal accessibility of low energy vibrational modes that may lead to distortion. Parallel NMRD and EPR studies on the three Gd(iii) complexes revealed good correspondence in estimating the electronic relaxation time. The Gd(iii) tris-pyridinecarboxylate complex possesses a very long electronic relaxation time making it a promising starting point for responsive gadolinium EPR probe design.

UR - http://www.scopus.com/inward/record.url?scp=85067186540&partnerID=8YFLogxK

U2 - 10.1039/c9dt01069f

DO - 10.1039/c9dt01069f

M3 - Article

VL - 48

SP - 8400

EP - 8409

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 23

ER -