Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities
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 parama...
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MDPI AG
2022-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/22/7836 |
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| author | Sergey P. Babailov Eugeny N. Zapolotsky Eduard S. Fomin Marina A. Polovkova Gayane A. Kirakosyan Alexander G. Martynov Yulia G. Gorbunova |
| author_facet | Sergey P. Babailov Eugeny N. Zapolotsky Eduard S. Fomin Marina A. Polovkova Gayane A. Kirakosyan Alexander G. Martynov Yulia G. Gorbunova |
| author_sort | Sergey P. Babailov |
| collection | DOAJ |
| description | 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 Ln<sub>2</sub>[(15C5)<sub>4</sub>Pc]<sub>3</sub> {where Ln = Tb (<b>1</b>) and Dy (<b>2</b>)} 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 <sup>1</sup>H NMR spectra indicates the similarity of the structure for the complexes <b>1</b> and <b>2</b> in solution of CDCl<sub>3</sub> and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu<sub>2</sub>[(15C5)<sub>4</sub>Pc]<sub>3</sub>. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes. |
| first_indexed | 2024-03-09T18:07:00Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T18:07:00Z |
| publishDate | 2022-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-7aa5049dcf52410e96d46c05bce5b8562023-11-24T09:21:58ZengMDPI AGMolecules1420-30492022-11-012722783610.3390/molecules27227836Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry PeculiaritiesSergey P. Babailov0Eugeny N. Zapolotsky1Eduard S. Fomin2Marina A. Polovkova3Gayane A. Kirakosyan4Alexander G. Martynov5Yulia G. Gorbunova6Nikolaev Institute of Inorganic Chemistry, The Siberian Branch of the Russian Academy of Sciences, Av. Lavrentyev 3, 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, The Siberian Branch of the Russian Academy of Sciences, Av. Lavrentyev 3, 630090 Novosibirsk, RussiaInstitute of Cytology and Genetics of the Siberian Branch of the Russian Academy of Sciences, Av. Lavrentyev 10, 630090 Novosibirsk, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Leninskii pr. 31-4, 119071 Moscow, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Leninskii pr. 31-4, 119071 Moscow, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Leninskii pr. 31-4, 119071 Moscow, RussiaFrumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Leninskii pr. 31-4, 119071 Moscow, RussiaThe 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 Ln<sub>2</sub>[(15C5)<sub>4</sub>Pc]<sub>3</sub> {where Ln = Tb (<b>1</b>) and Dy (<b>2</b>)} 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 <sup>1</sup>H NMR spectra indicates the similarity of the structure for the complexes <b>1</b> and <b>2</b> in solution of CDCl<sub>3</sub> and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu<sub>2</sub>[(15C5)<sub>4</sub>Pc]<sub>3</sub>. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes.https://www.mdpi.com/1420-3049/27/22/7836NMR spectroscopylanthanidesphthalocyaninessymmetrypseudo-contact contribution of lanthanide-induced shifts |
| spellingShingle | Sergey P. Babailov Eugeny N. Zapolotsky Eduard S. Fomin Marina A. Polovkova Gayane A. Kirakosyan Alexander G. Martynov Yulia G. Gorbunova Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities Molecules NMR spectroscopy lanthanides phthalocyanines symmetry pseudo-contact contribution of lanthanide-induced shifts |
| title | Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities |
| title_full | Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities |
| title_fullStr | Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities |
| title_full_unstemmed | Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities |
| title_short | Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities |
| title_sort | structure determination of binuclear triple decker phthalocyaninato complexes by nmr via paramagnetic shifts analysis using symmetry peculiarities |
| topic | NMR spectroscopy lanthanides phthalocyanines symmetry pseudo-contact contribution of lanthanide-induced shifts |
| url | https://www.mdpi.com/1420-3049/27/22/7836 |
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