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LnDOTA puppeteering: removing the water molecule and imposing tetragonal symmetry

Manvell, Anna Schannong; Pfleger, Rouven ORCID iD icon 1; Bonde, Niels Andreas; Briganti, Matteo; Mattei, Carlo Andrea; Nannestad, Theis Brock; Weihe, Høgni; Powell, Annie K. 1; Ollivier, Jacques; Bendix, Jesper; Perfetti, Mauro
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)

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 C$_4$ 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. ... mehr


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Originalveröffentlichung
DOI: 10.1039/D3SC03928E
Scopus
Zitationen: 3
Web of Science
Zitationen: 2
Dimensions
Zitationen: 5
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 07.01.2024
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000166980
Erschienen in Chemical Science
Verlag Royal Society of Chemistry (RSC)
Band 15
Heft 1
Seiten 113–123
Vorab online veröffentlicht am 12.12.2023
Nachgewiesen in Dimensions
Web of Science
Scopus
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