Issue 1, 2024

LnDOTA puppeteering: removing the water molecule and imposing tetragonal symmetry

Abstract

Complexes of lanthanide(III) ions (Ln) with tetraazacyclododecane-N,N′,N′′,N′′′-tetraacetate (DOTA) are a benchmark in the field of magnetism due to their well-investigated and sometimes surprising features. Ab initio calculations suggest that the ninth ligand, an axial water molecule, is key in defining the magnetic properties because it breaks the potential C4 symmetry of the resulting complexes. In this paper, we experimentally isolate the role of the water molecule by excluding it from the metal coordination sphere without altering the chemical structure of the ligand. Our complexes are therefore designed to be geometrically tetragonal and strict crystallographic symmetry is achieved by exploiting a combination of solution ionic strength and solid state packing effects. A thorough multitechnique approach has been used to unravel the electronic structure and magnetic anisotropy of the complexes. Moreover, the geometry enhancement allows us to predict, using only one angle obtained from the crystal structure, the ground state composition of all the studied derivatives (Ln = Tb to Yb). Therefore, these systems also provide an excellent platform to test the validity and limitations of the ab initio methods. Our combined experimental and theoretical investigation proves that the water molecule is indeed key in defining the magnetic anisotropy and the slow relaxation of these complexes.

Graphical abstract: LnDOTA puppeteering: removing the water molecule and imposing tetragonal symmetry

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Jul 2023
Accepted
25 Oct 2023
First published
12 Dec 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 113-123

LnDOTA puppeteering: removing the water molecule and imposing tetragonal symmetry

A. S. Manvell, R. Pfleger, N. A. Bonde, M. Briganti, C. A. Mattei, T. B. Nannestad, H. Weihe, A. K. Powell, J. Ollivier, J. Bendix and M. Perfetti, Chem. Sci., 2024, 15, 113 DOI: 10.1039/D3SC03928E

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