Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities

Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities Full article

Journal

Molecules
ISSN: 1420-3049

Output data

Year: 2022, Volume: 27, Number: 22, Article number : 7836, Pages count : 10 DOI: 10.3390/molecules27227836

Authors

Babailov Sergey P. ¹ , Zapolotsky Eugeny N. ¹ , Fomin Eduard S. ² , Polovkova Marina A. ³ , Kirakosyan Gayane A. ^3,4 , Martynov Alexander G. ³ , Gorbunova Yulia G. ^3,4

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences
2	Institute of Cytology and Genetics, SB RAS
3	Frumkin Institute of Physical Chemistry and Electrochemistry
4	Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide complexes in solution, using NMR is a difficult task, since several paramagnetic centers act simultaneously on the resulting chemical shift of a particular nucleus. In this paper, we have demonstrated the possibility of molecular structure determination in solution on the example of binuclear triple-decker lanthanide(III) complexes with tetra-15-crown-5-phthalocyanine Ln2[(15C5)4Pc]3 {where Ln = Tb (1) and Dy (2)} by quantitative analysis of the pseudo-contact lanthanide-induced shifts (LIS). The symmetry of complexes was used for the simplification of the calculation of pseudo-contact shifts on the base of the expression for the magnetic susceptibility tensor in the arbitrary oriented magnetic axis system. Good agreement between the calculated and experimental shifts in the 1H NMR spectra indicates the similarity of the structure for the complexes 1 and 2 in solution of CDCl3 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu2[(15C5)4Pc]3. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes.

Babailov S.P. , Zapolotsky E.N. , Fomin E.S. , Polovkova M.A. , Kirakosyan G.A. , Martynov A.G. , Gorbunova Y.G.
Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities
Molecules. 2022. V.27. N22. 7836 :1-10. DOI: 10.3390/molecules27227836 WOS Scopus РИНЦ OpenAlex

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