An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides
New complexes of manganese(II) hexafluoroacetylacetonate [Mn(hfac)<sub>2</sub>] with 2-(1-<i>R</i>-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (<i>R</i> = CHF<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>F, CH&l...
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2023-10-01
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| author | Ekaterina Kudryavtseva Andrey Serykh Bogdan Ugrak Tatyana Dutova Darina Nasyrova Alexander Korlyukov Mikhail Zykin Nikolay Efimov Artem Bogomyakov Evgeny Tretyakov |
| author_facet | Ekaterina Kudryavtseva Andrey Serykh Bogdan Ugrak Tatyana Dutova Darina Nasyrova Alexander Korlyukov Mikhail Zykin Nikolay Efimov Artem Bogomyakov Evgeny Tretyakov |
| author_sort | Ekaterina Kudryavtseva |
| collection | DOAJ |
| description | New complexes of manganese(II) hexafluoroacetylacetonate [Mn(hfac)<sub>2</sub>] with 2-(1-<i>R</i>-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (<i>R</i> = CHF<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>F, CH<sub>2</sub>CHF<sub>2</sub> or CH<sub>2</sub>CF<sub>3</sub>) were synthesised and characterised structurally and magnetically. All complexes were prepared under similar conditions. Nonetheless, their crystal structures were considerably different. Depending on the structure of fluorinated alkyl substituent <i>R</i>, the complexation reaction led to complexes of three types: chain-polymeric complexes with the head-to-head or head-to-tail motif and complexes of molecular structure. All complexes show strong antiferromagnetic behaviour in a high-temperature region (150–300 K) and weak ferro- or antiferromagnetic exchange interactions at low temperatures. The stronger antiferromagnetic exchange, −101.7 ± 1.5 or −136 ± 10 cm<sup>−1</sup>, −82.3 ± 1.3 cm<sup>−1</sup> and −87.4 ± 1.3 cm<sup>−1</sup>, was attributed to the magnetic interaction in three- or two-spin clusters: {>N∸O–Mn<sup>2+</sup>–O∸N<} or {>N∸O–Mn<sup>2+</sup>}, respectively. The weaker antiferromagnetic interaction, −0.005, between three-spin clusters or ferromagnetic interactions, 0.18–0.81 cm<sup>−1</sup>, between two-spin clusters are realised through the pyrazole ring or intermolecular contacts. |
| first_indexed | 2024-03-10T21:20:13Z |
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| id | doaj.art-fb6d21d6211245fcb54bdce3ceabde73 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-10T21:20:13Z |
| publishDate | 2023-10-01 |
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| series | Crystals |
| spelling | doaj.art-fb6d21d6211245fcb54bdce3ceabde732023-11-19T16:10:34ZengMDPI AGCrystals2073-43522023-10-011310152810.3390/cryst13101528An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl NitroxidesEkaterina Kudryavtseva0Andrey Serykh1Bogdan Ugrak2Tatyana Dutova3Darina Nasyrova4Alexander Korlyukov5Mikhail Zykin6Nikolay Efimov7Artem Bogomyakov8Evgeny Tretyakov9N. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, 28 Vavilov Str., 119991 Moscow, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Leninsky Ave. 31, 119991 Moscow, RussiaN. S. Kurnakov Institute of General and Inorganic Chemistry, Leninsky Ave. 31, 119991 Moscow, RussiaInternational Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3a, 630090 Novosibirsk, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Ave. 47, 119991 Moscow, RussiaNew complexes of manganese(II) hexafluoroacetylacetonate [Mn(hfac)<sub>2</sub>] with 2-(1-<i>R</i>-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (<i>R</i> = CHF<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>F, CH<sub>2</sub>CHF<sub>2</sub> or CH<sub>2</sub>CF<sub>3</sub>) were synthesised and characterised structurally and magnetically. All complexes were prepared under similar conditions. Nonetheless, their crystal structures were considerably different. Depending on the structure of fluorinated alkyl substituent <i>R</i>, the complexation reaction led to complexes of three types: chain-polymeric complexes with the head-to-head or head-to-tail motif and complexes of molecular structure. All complexes show strong antiferromagnetic behaviour in a high-temperature region (150–300 K) and weak ferro- or antiferromagnetic exchange interactions at low temperatures. The stronger antiferromagnetic exchange, −101.7 ± 1.5 or −136 ± 10 cm<sup>−1</sup>, −82.3 ± 1.3 cm<sup>−1</sup> and −87.4 ± 1.3 cm<sup>−1</sup>, was attributed to the magnetic interaction in three- or two-spin clusters: {>N∸O–Mn<sup>2+</sup>–O∸N<} or {>N∸O–Mn<sup>2+</sup>}, respectively. The weaker antiferromagnetic interaction, −0.005, between three-spin clusters or ferromagnetic interactions, 0.18–0.81 cm<sup>−1</sup>, between two-spin clusters are realised through the pyrazole ring or intermolecular contacts.https://www.mdpi.com/2073-4352/13/10/1528nitronyl nitroxidesmetal–nitroxide complexescrystal structuresmagnetic properties |
| spellingShingle | Ekaterina Kudryavtseva Andrey Serykh Bogdan Ugrak Tatyana Dutova Darina Nasyrova Alexander Korlyukov Mikhail Zykin Nikolay Efimov Artem Bogomyakov Evgeny Tretyakov An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides Crystals nitronyl nitroxides metal–nitroxide complexes crystal structures magnetic properties |
| title | An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides |
| title_full | An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides |
| title_fullStr | An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides |
| title_full_unstemmed | An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides |
| title_short | An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides |
| title_sort | influence of fluorinated alkyl substituents on structure and magnetic properties of mn ii complexes with pyrazolyl substituted nitronyl nitroxides |
| topic | nitronyl nitroxides metal–nitroxide complexes crystal structures magnetic properties |
| url | https://www.mdpi.com/2073-4352/13/10/1528 |
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