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

doi:10.1039/c9dt01069f

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

Authors

Elizaveta A. Suturina

Kevin Mason

Mauro Botta

Fabio Carniato

Ilya Kuprov

Nicholas F. Chilton

Eric J.L. McInnes

Michele Vonci

Professor David Parker david.parker@durham.ac.uk
Emeritus Professor

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.

Citation

Suturina, E. A., Mason, K., Botta, M., Carniato, F., Kuprov, I., Chilton, N. F., …Parker, D. (2019). Periodic trends and hidden dynamics of magnetic properties in three series of triazacyclononane lanthanide complexes. Dalton Transactions, 48(23), 8400-8409. https://doi.org/10.1039/c9dt01069f

Journal Article Type	Article
Publication Date	Jun 1, 2019
Deposit Date	Jun 27, 2019
Publicly Available Date	Jun 1, 2020
Journal	Dalton Transactions
Print ISSN	1477-9226
Electronic ISSN	1477-9234
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	48
Issue	23
Pages	8400-8409
DOI	https://doi.org/10.1039/c9dt01069f