Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes

Svetlana S Degtyareva; Daniil A Bardonov; Anna V Afanaseva; Lada N Puntus; Konstantin A Lyssenko; Kirill P Birin; Mikhail E Minyaev; Julia V Burykina; Ilya V Taydakov; Evgenia A Varaksina; Ilya E Nifant'ev; Dmitrii M Roitershtein

doi:10.1021/acs.inorgchem.3c03492

Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes

Inorg Chem. 2024 Jan 29;63(4):1867-1878. doi: 10.1021/acs.inorgchem.3c03492. Epub 2024 Jan 18.

Authors

Svetlana S Degtyareva^{1

2}, Daniil A Bardonov^{1

2}, Anna V Afanaseva^{1

2}, Lada N Puntus^{1

3}, Konstantin A Lyssenko⁴, Kirill P Birin⁵, Mikhail E Minyaev^{1

6}, Julia V Burykina⁶, Ilya V Taydakov^{1

7}, Evgenia A Varaksina^{1

7}, Ilya E Nifant'ev^{1

4}, Dmitrii M Roitershtein^{1

2

6}

Affiliations

¹ A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
² National Research University Higher School of Economics (HSE University), 101000 Moscow, Russian Federation.
³ V.A. Kotel'nikov Institute of Radioengineering and Electronics, Russian Academy of Sciences, Fryazino, 141190 Moscow, Russian Federation.
⁴ Department of Chemistry, M.V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation.
⁵ A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071 Moscow, Russian Federation.
⁶ N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
⁷ P.N. Lebedev Physical Institute, Russian Academy of Sciences, 119991 Moscow, Russian Federation.

PMID: 38237143
DOI: 10.1021/acs.inorgchem.3c03492

Abstract

LnCl₃(THF)₃ (Ln = Y, La ÷ Nd, Sm ÷ Lu) readily react with the tridentate 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me₃tach) ligand to form mono- or binuclear lanthanide trichloride complexes, depending on the stoichiometry of the reaction and the ionic radius of the metal: mononuclear pseudosandwich [LnCl₃(Me₃tach)₂], (Ln = Y, La ÷ Ho) or binuclear complexes [Ln₂Cl₆(Me₃tach)₃], or [LnCl₃(Me₃tach)(THF)]₂ (Ln = Sm, Tb). Detailed analysis of the NMR data of [LnCl₃(Me₃tach)₂] complexes with paramagnetic lanthanide ions showed that their structures remained unchanged in the toluene solution. A series of isomorphous complexes [LnCl₃(Me₃tach)(Py)₂] (Ln = La, Sm, Tb, Er, Lu; Py = pyridine) have been obtained by the recrystallization of either mononuclear or binuclear complexes from pyridine. Complexes of terbium and europium ions with the Me₃tach ligand exhibit relatively high quantum yields of metal-centered luminescence (0.39 and 0.32, respectively).